CN106978595B - 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 PDF

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CN106978595B
CN106978595B CN201710220962.1A CN201710220962A CN106978595B CN 106978595 B CN106978595 B CN 106978595B CN 201710220962 A CN201710220962 A CN 201710220962A CN 106978595 B CN106978595 B CN 106978595B
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carbon nitride
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CN106978595A (en
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向琴
张凯
宫建茹
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National Center for Nanosccience and Technology China
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Abstract

The invention discloses a kind of graphite type carbon nitride nanotube array photoelectrode, preparation method and as light anode solar energy electrochemical decomposition aquatic products oxygen purposes, the diameter and length of graphite type carbon nitride nanotube in graphite type carbon nitride nanotube array photoelectrode of the invention are adjustable, diameter range is 20nm-170nm, length range 400nm-2500nm.Graphite type carbon nitride nanotube array photoelectrode of the invention is using the anodised aluminium of conductive substrates support as template, and using the cyanamide solution of concentration as presoma, high-temperature polycondensation is obtained in an inert atmosphere.Graphite type carbon nitride nanotube array photoelectrode of the invention possesses big specific surface area, more surface-active site, is applied to solar energy electrochemical decomposition aquatic products oxygen as light anode and has excellent performance.

Description

A kind of graphite type carbon nitride nanotube array photoelectrode, preparation method and the usage
Technical field
The invention belongs to organic semiconducting materials and field of nanometer technology, are 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, preparation method and As light anode solar energy electrochemical decomposition aquatic products oxygen purposes.
Background technique
Graphite type carbon nitride (referred to as g-CN) is that one kind is only partly led by the polymer that two kinds of nonmetalloids of C and N are constituted Body is widely used in light degradation pollutant, photocatalysis point since it is with visible light-responded, rich and easy to get, non-toxic stable Solve aquatic products hydrogen field.So far, have comprising a variety of nanostructures including mesoporous g-CN, g-CN nanometer rods, g-CN nanotube G-CN photochemical catalyst is seen in report.They generally possess biggish specific surface area and more surface-active site, thus show Very excellent photocatalysis performance out.
The correlative study exploration work for being applied to optical electro-chemistry decomposition water using g-CN as optoelectronic pole is still at an early stage, The efficiency that optical electro-chemistry decomposes 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 film in conductive substrates, and still, resulting optoelectronic pole is in 0.1M Na2SO4In solution, 1.23V When 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, for the optoelectronic pole that both methods obtains without special nanostructure, specific surface area is less than normal, causes electron hole can not It efficiently separates, and then photoelectric properties are very low.
So preparation has the g-CN optoelectronic pole of special nanostructure, to increase the specific surface area of optoelectronic pole, shorten a small number of The collection distance of carrier, so that the utilization efficiency for promoting electrode interior photo-generated carrier is significant.
Summary of the invention
For the above-mentioned problems in the prior art, it is an object of that present invention to provide a kind of graphite type carbon nitride nanotubes Array photoelectric pole, preparation method and the usage.Graphite mould nitrogen in graphite type carbon nitride nanotube array photoelectrode of the invention Carbon nano tube length and caliber are adjustable, and the nanotube array photoelectrode possesses biggish specific surface area, more active sites Point, while the hollow one-dimentional structure of nanotube is also conducive to the separation of electron hole.Graphite type carbon nitride nanotube of the 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。
In order to achieve the above object, the invention adopts the 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 Nanotube array photoelectrode is made of substrate and the graphite type carbon nitride nano-tube array in the substrate, 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 graphite type carbon nitride nanotube array photoelectrode of the 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 graphite type carbon nitride nanotube of the invention be it is nanotube-shaped, chemical composition be graphite mould C3N4。
Preferably, the diameter of the graphite type carbon nitride nanotube be 20nm-170nm, 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 piece.
Second aspect, the present invention provide 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 film, encapsulation on adhesion layer；
(3) electrode that step (2) encapsulation obtains is placed in electrolyte, carries out anodic oxidation；
(4) electrode that step (3) anodic oxidation obtains is placed in H3PO4Reaming in solution obtains the anodic oxygen of substrate support Change aluminum alloy pattern plate；
(5) removal encapsulates, and pours into cyanamide in the anodic oxidation aluminium formwork of the substrate support obtained to step (4), obtains base The template for pouring into cyanamide of bottom support；
(6) it is sealed processing, is then annealed under inert gas protection；
(7) removing template is removed, graphite type carbon nitride nanotube array photoelectrode is obtained.
In the present invention, after step (3) anodic oxidation, porous aluminas and fine and close alumina flake, aluminium oxide are obtained Thin layer becomes barrier layer between porous aluminas and adhesion 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 fine and close alumina barrier layer.
Preferably, step (1) substrate is conductive substrates, preferably any in ito glass, FTO glass or Si piece It is a kind of.
Preferably, the step of step (1) described substrate is first cleaned by ultrasonic and is dried up before the use.
Preferably, step (1) described adhesion layer with a thickness of 5nm-70nm, for example, 5nm, 10nm, 20nm, 25nm, 30nm, 35nm, 40nm, 45nm, 50nm, 60nm or 70nm etc..
Preferably, step (1) adhesion layer is TiO2Layer, or for by Ti layers and the W layers of combination layer constituted.
Preferably, step (1) adhesion layer is TiO2Layer, and the TiO2Layer with a thickness of 20nm-50nm.
Preferably, step (1) adhesion layer is the TiO of 30nm thickness2Layer.
Preferably, step (1) adhesion layer is by Ti layers and the W layers of combination layer constituted, and the Ti in the combination layer Layer with a thickness of 5nm-10nm, described W layers with a thickness of 40nm-70nm.
Preferably, step (1) adhesion layer is the combination layer being made of the W layer of the Ti layer of 10nm thickness and 60nm thickness.
Preferably, when step (1) adhesion layer is TiO2When layer, TiO has been sputtered in step (1)2After layer, step (2) It before sputtering Al film, proceeds 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 30min-4h, example For example 30min, 1h, 2h, 2.5h, 3h or 4h etc., preferably 2h.
Preferably, to having sputtered TiO2During the substrate of layer is made annealing treatment, it is warming up to the heating of annealing temperature Rate 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, step (2) the Al film with a thickness of 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) encapsulation are as follows: the electrode after sputtering Al film is packaged and is solidified using silica gel.
Preferably, step (3) 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 mixed solution of alcoholic solution and oxalic acid aqueous solution, the preferably oxalic acid aqueous solution of 0.2M-0.4M, the phosphoric acid water of 5wt%-10wt% Solution, it is any one in the sulfuric acid water-alcohol solution or citric acid water alcoholic solution of 0.5M-1M and the mixed solution of 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 the sulfuric acid of 98wt% with Water and alcohol mixing, make the molar concentration 0.5M-1M of sulfuric acid water-alcohol solution.
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, obtains the citric acid water alcoholic solution of 0.15M, then by the citric acid water alcoholic solution of 0.15M and The oxalic acid aqueous solution of 0.3M is mixed according to volume ratio 10:1-60:1.
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.
" phosphate aqueous solution of 5wt%-10wt% " 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 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 type of suitably selected electrolyte and the voltage of anode oxidation process, and cooperate 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 solution is illustrated:
One of optimal technical scheme as the method for the invention, when the electrolyte that step (3) uses is 0.2M-0.4M Oxalic acid when, during carrying out anodic oxidation, voltage 30V-60V, cooperation adjusts other of the invention technological parameters, 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) uses is the oxalic acid of 0.3M, during carrying out anodic oxidation, voltage For 40V, cooperation adjusts other technological parameters of the invention, can make in graphite type carbon nitride nanotube array photoelectrode of the invention The length of graphite type carbon nitride nanotube is in 400nm-1600nm, and diameter is in 70nm.
Preferably, when the electrolyte that step (3) uses is the phosphoric acid solution of 5wt%-10wt%, anodic oxidation is carried out In the process, voltage 70V-100V, cooperation adjust other technological parameters of the invention, can make graphite type carbon nitride nanometer of the 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) uses is the phosphoric acid solution of 5wt%, during carrying out anodic oxidation, Voltage is 86V, and cooperation adjusts other technological parameters of the invention, can make graphite type carbon nitride nanotube array photoelectrode of the invention In graphite type carbon nitride nanotube length in 400nm-1600nm, diameter is in 150nm.
Preferably, when the electrolyte that step (3) uses is the sulfuric acid water-alcohol solution of 0.5M-1M, anodic oxidation is carried out In the process, voltage 10V-25V, cooperation adjust other technological parameters of the invention, can make graphite type carbon nitride nanometer of the 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) uses is the sulfuric acid water-alcohol solution of 0.55M, the mistake of anodic oxidation is carried out Cheng Zhong, voltage 20V, cooperation adjust other technological parameters of the invention, can make graphite type carbon nitride nano-tube array of the 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) uses is the mixed solution of citric acid water alcoholic solution and oxalic acid aqueous solution, During carrying out anodic oxidation, voltage 90V-120V, cooperation adjusts other technological parameters of the invention, can make stone of the 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) uses is the mixed solution of citric acid water alcoholic solution and oxalic acid aqueous solution, During carrying out anodic oxidation, voltage 120V, cooperation adjusts other technological parameters of the invention, can make graphite mould of the 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., preferably 80min-140min。
Preferably, cyanamide is poured into the anodic oxidation aluminium formwork of step (5) substrate support obtained to step (4) Process are as follows: the anodic oxidation aluminium formwork of substrate support is immersed in cyanamide solution, ultrasound, obtain 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 obtains by the following method: the cyanamide water for being 50wt% by mass fraction Solution is placed 3 days in 50 DEG C of vacuum drying ovens, the cyanamide solution being concentrated.
Preferably, the time of the ultrasound be 5min-10min, for example, 5min, 6min, 7min, 8min, 9min or 10min etc..
Preferably, the process of step (6) described encapsulation process are as follows: the cover one in the template 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 uses is preferably ceramic crucible.
Preferably, step (6) inert gas be helium, neon, argon gas, Krypton or xenon in any one or extremely Few two kinds of gaseous mixture, preferably argon gas.
Preferably, step (6) described inert gas be passed through speed be 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 3h-6h, such as 3h, 3.5h, 4h, 4.5h, 5h Or 6h etc., preferably 4h.
Preferably, step (6) be warming up to the annealing temperature heating rate be 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) process for removing removing template are as follows: the electrode after step (7) annealing is immersed into 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, the 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, the method also includes after step (5) step (6) it Preceding progress step (5) ': the cyanamide solution of the template surface for pouring into cyanamide of substrate support is removed.
Preferably, the method also includes carrying out step (6) ' before the step (7) after step (6): cooling down and closes 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) it anneals to the conductive substrates for having sputtered adhesion layer；
(3) continue to sputter Al film on adhesion layer, obtain Al/ adhesion layer/conductive substrates, encapsulate；
(4) electrode that step (3) encapsulation obtains is placed in electrolyte, anode is carried out under the voltage conditions of 20V-120V Oxidation；
(5) electrode that step (4) anodic oxidation obtains is placed in H3PO4Reaming 40min-300min in solution, obtains substrate The anodic oxidation aluminium formwork of support is named as through-hole AAO template/adhesion layer/conductive substrates；
(6) silica gel for removing encapsulated electrode, immerses in cyanamide solution, and ultrasound obtains the mould for pouring into cyanamide of substrate support Plate is named as cyanamide-AAO/ adhesion layer/conductive substrates；
(7) in the template for pouring into cyanamide of substrate support the sizes such as one piece of cover glass, sealed with tinfoil, in argon gas It in 550 DEG C of annealing 4h under protection, is cooled to room temperature, 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, 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 film on adhesion layer, use silica gel packaging, solidification；
(4) electrode that step (3) encapsulation obtains is placed in electrolyte, anode is carried out under the voltage conditions of 20V-120V Oxidation；
(5) electrode that step (4) anodic oxidation obtains is placed in H3PO4Reaming 40min-300min in solution, obtains substrate The anodic oxidation aluminium formwork of support；
(6) the cyanamide aqueous solution that mass fraction is 50wt% is placed 3 days in 50 DEG C of vacuum drying ovens, the ammonia being concentrated Nitrile solution；
(7) silica gel for removing encapsulated electrode, immerses in the cyanamide solution of above-mentioned concentration, and ultrasound obtains substrate support Pour into the template of cyanamide；
(8) then the cyanamide solution for removing the template surface for pouring into cyanamide of substrate support pours into ammonia in substrate support The glass of the sizes such as one piece of cover, is encased with tinfoil, is then placed in ceramic crucible in the template of nitrile, then with tinfoil that crucible is close Envelope, under protection of argon gas in 550 DEG C of annealing 4h, is cooled to room temperature, and closing is passed through argon gas；
(9) electrode after step (8) annealing 3h-12h in the NaOH of 0.12M is immersed to obtain to remove removing template Graphite type carbon nitride nanotube array photoelectrode.
The third aspect, the present invention provide graphite type carbon nitride nanotube array photoelectrode as described in relation to the first aspect as light Purposes of the anode in solar energy electrochemical decomposition aquatic products oxygen.
Compared with the prior art, the invention has the following beneficial effects:
(1) anodised aluminium that method of the invention is supported using conductive substrates is template, before the cyanamide solution with concentration is Body is driven, high-temperature polycondensation obtains in an inert atmosphere, by adjusting Arrays Aluminum Films in Acid Solution, voltage in anode oxidation process, Yi Jiyu The cooperation of other parameters has been obtained by diameter, length is adjustable, and graphite type carbon nitride nanotube is regular is arranged in shape in conductive substrates At graphite type carbon nitride nanotube array photoelectrode, the diameter range of graphite type carbon nitride nanotube is 20nm-170nm, long Degree range is 400nm-2500nm.
(2) graphite type carbon nitride nanotube array photoelectrode prepared by the present invention has big specific surface area, more table Face active site, and the hollow one-dimentional structure of the graphite type carbon nitride nanotube of regular arrangement is conducive to point of 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 is had 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 regulate and control.
Detailed description of the invention
Fig. 1 is the preparation flow schematic diagram that the present invention prepares g-CN nanotube array photoelectrode；
Fig. 2 is the SEM sectional view of g-CN nanotube array photoelectrode prepared by embodiment 2；
Fig. 3 is the SEM plan view of g-CN nanotube array photoelectrode prepared by embodiment 3；
Fig. 4 is the SEM sectional view of g-CN nanotube array photoelectrode prepared by embodiment 3；
Fig. 5 is the photoelectric properties figure of g-CN nanotube array photoelectrode prepared by embodiment 3；
Fig. 6 is the SEM sectional view of g-CN nanotube array photoelectrode prepared by embodiment 4.
Specific embodiment
To further illustrate the technical scheme of the present invention below with reference to the accompanying drawings and specific embodiments.
Embodiment 1
(1) FTO is cut into 2cm*2.5cm size, successively each ultrasound 15min in isopropanol, acetone and ethyl alcohol, Then with being dried with nitrogen.
(2) clean one end FTO is stained with high temperature gummed tape, the TiO of 30nm thickness is then sputtered on FTO2, sputtering terminates Afterwards, it tears high temperature gummed tape, places it in Muffle furnace, 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 to sputter The aluminium of 1600nm, after taking-up, adhesive tape of tearing is labeled as Al/TiO2/FTO。
(4) silica gel packaging Al/TiO is used2/ FTO electrode, is then stood 2-5 days, silica gel is allowed sufficiently to solidify.
(5) electrode prepared by step (4) is placed in 0.3M H2C2O4In solution, anodic oxidation is carried out, oxidation voltage is 40V when anodic oxidation is transparent to electrode, terminates oxidation, is then immersed in 5wt%H3PO4In solution, reaming 120min is obtained The anodic oxidation aluminium formwork of substrate support is labeled as AAO-O/TiO2/ FTO, wherein the aperture of anodic oxidation aluminium formwork is about 70nm。
(6) silica gel for removing encapsulated electrode, is put into the cyanamide solution of concentration that (the cyanamide aqueous solution of 50wt% is at 50 DEG C Placed 3 days in vacuum drying oven), the ultrasound 10min, power 100w in ultrasonic cleaner.It after ultrasound, takes out, removes Then the cyanamide solution of excess surface the sheet glass of the sizes such as one piece and encases sealing with tinfoil in its surface cover, then will It is put into ceramic crucible, then is sealed ceramic crucible with tinfoil.
(7) crucible being sealed 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, and is cooled to room temperature to temperature, closes gas, takes out sample.The sample that reaction obtains is placed in 7h is impregnated in 0.12M NaOH solution, is removed template, is obtained g-CN nanometer pipe array electrode, wherein g-CN nanotube is averaged Caliber about 70nm, length 1600nm.
Embodiment 2
(1) FTO is cut into 2cm*2.5cm size, successively each ultrasound 15min in isopropanol, acetone and ethyl alcohol, Then with being dried with nitrogen.
(2) clean one end FTO is stained with high temperature gummed tape, the TiO of 30nm thickness is then sputtered on FTO2As adherency Layer, after sputtering, high temperature gummed tape of tearing is placed it 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 to sputter The aluminium of 800nm, after taking-up, adhesive tape of tearing is labeled as Al/TiO2/FTO。
(4) silica gel packaging Al/TiO is used2/ FTO electrode, is then stood 2-5 days, silica gel is allowed sufficiently to solidify.
(5) electrode prepared by step (4) is placed in 5wt%H3PO4In solution, oxidation voltage 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, is labeled as AAO-p/TiO2/ FTO, wherein the aperture of anodic oxidation aluminium formwork is about 150nm.
(6) silica gel for removing encapsulated electrode, is put into the cyanamide solution of concentration that (the cyanamide aqueous solution of 50wt% is at 50 DEG C Placed 3 days in vacuum drying oven), the ultrasound 10min, power 100w in ultrasonic cleaner.It after ultrasound, takes out, removes Then the cyanamide solution of excess surface the sheet glass of the sizes such as one piece and encases sealing with tinfoil in its surface cover, then will It is put into ceramic crucible, then is sealed ceramic crucible with tinfoil.
(7) crucible being sealed 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, and is cooled to room temperature to temperature, closes gas, takes out sample.The sample that reaction obtains is placed in 6h is impregnated in 0.12M NaOH solution, is removed template, is obtained g-CN nanometer pipe array electrode, wherein g-CN nanotube is averaged Caliber about 150nm.
Fig. 2 is the SEM sectional view of the g-CN nanotube array photoelectrode of this example preparation, as seen from the figure, average straight Diameter is 150nm, and the g-CN nano-tube array that length is 800nm is basically perpendicular to substrate.
Embodiment 3
(1) FTO is cut into 2cm*2.5cm size, successively each ultrasound 15min in isopropanol, acetone and ethyl alcohol, Then with being dried with nitrogen.
(2) clean one end FTO is stained with high temperature gummed tape, the TiO of 30nm thickness is then sputtered on FTO2, sputtering terminates Afterwards, it tears high temperature gummed tape, places it in Muffle furnace, 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 to sputter The aluminium of 1600nm, after taking-up, adhesive tape of tearing is labeled as Al/TiO2/FTO。
(4) silica gel packaging Al/TiO is used2/ FTO electrode, is then stood 2-5 days, silica gel is allowed sufficiently to solidify.
(5) electrode prepared by step (4) is placed in 5wt%H3PO4In solution, oxidation voltage 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, is labeled as AAO-p/TiO2/ FTO, wherein the aperture of anodic oxidation aluminium formwork is about 150nm.
(6) silica gel for removing encapsulated electrode, is put into the cyanamide solution of concentration that (the cyanamide aqueous solution of 50wt% is at 50 DEG C Placed 3 days in vacuum drying oven), the ultrasound 10min, power 100w in ultrasonic cleaner.It after ultrasound, takes out, removes Then the cyanamide solution of excess surface the sheet glass of the sizes such as one piece and encases sealing with tinfoil in its surface cover, then will It is put into ceramic crucible, then is sealed ceramic crucible with tinfoil.
(7) crucible being sealed 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, and is cooled to room temperature to temperature, closes gas, takes out sample.The sample that reaction obtains is placed in 12h is impregnated in 0.12M NaOH solution, is removed template, is obtained g-CN nanometer pipe array electrode, wherein g-CN nanotube is averaged Caliber about 150nm.
Fig. 3 is the SEM plan view of the g-CN nanotube array photoelectrode of this example preparation, as seen from the figure, nanotube Top it is opening-like.
Fig. 4 is the SEM sectional view of the g-CN nanotube array photoelectrode of this example preparation, as seen from the figure, average straight Diameter is 150nm, and the g-CN nano-tube array that length is 1600nm is basically perpendicular to substrate.
Fig. 5 is the photoelectric properties figure of the g-CN nanotube array photoelectrode of this example preparation, as seen from the figure, When 1.23V vsRHE, in 0.1M Na2SO4In solution, g-CN nanotube array photoelectrode photoelectric current manufactured in the present embodiment is reachable To 94 μ A/cm2。
Embodiment 4
(1) ITO is cut into 2cm*2.5cm size, successively each ultrasound 15min in isopropanol, acetone and ethyl alcohol, Then with being dried with nitrogen.
(2) clean one end ITO is stained with high temperature gummed tape, Ti, 60nm that 10nm thickness is then successively sputtered on ITO are thick W, 400nm thickness Al, be labeled as Al/W/Ti/ITO.
(3) silica gel packaging Al/W/Ti/ITO electrode is used, 2-5 days is then stood, silica gel is allowed sufficiently to solidify.
(4) electrode prepared by step (3) is placed in 5wt%H3PO4In solution, oxidation voltage 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, is labeled as AAO-P/W/Ti/ITO, wherein the aperture of anodic oxidation aluminium formwork is about 150nm.
(5) silica gel for removing encapsulated electrode, is put into the cyanamide solution of concentration that (the cyanamide aqueous solution of 50wt% is at 50 DEG C Placed 3 days in vacuum drying oven), the ultrasound 5min, power 100w in ultrasonic cleaner.It after ultrasound, takes out, removes table Then the extra cyanamide solution in face the sheet glass of the sizes such as one piece and encases sealing with tinfoil in its surface cover, then by it It is put into ceramic crucible, then is sealed ceramic crucible with tinfoil.
(6) crucible being sealed 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, and is cooled to room temperature to temperature, closes gas, takes out sample.The sample that reaction obtains is placed in 3h is impregnated in 0.12M NaOH solution, is removed template, is obtained g-CN nanometer pipe array electrode, wherein g-CN nanotube is averaged Caliber about 150nm.
Fig. 6 is the SEM sectional view of the g-CN nanotube array photoelectrode of this example preparation, as seen from the figure, average straight Diameter is 150nm, and length is the g-CN nano-tube array of 400nm perpendicular to substrate.
Embodiment 5
(1) FTO is cut into 2cm*2.5cm size, successively each ultrasound 10min in isopropanol, acetone and ethyl alcohol, Then with being dried with nitrogen.
(2) clean one end FTO is stained with high temperature gummed tape, the TiO of 25nm is then sputtered on FTO2, sputtering terminates Afterwards, it tears high temperature gummed tape, places it in Muffle furnace, anneal 2h at 500 DEG C, and 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 to sputter The aluminium of 600nm, after taking-up, adhesive tape of tearing is labeled as Al/TiO2/FTO。
(4) silica gel packaging Al/TiO is used2/ FTO electrode, is then stood 2-5 days, silica gel is allowed sufficiently to solidify.
(5) electrode prepared by step (4) is placed in 0.3M H2C2O4In solution, anodic oxidation is carried out, oxidation voltage is 50V when anodic oxidation is transparent to electrode, terminates oxidation, is then immersed in 5wt%H3PO4In solution, reaming 90min is obtained The anodic oxidation aluminium formwork of substrate support is labeled as AAO-O/TiO2/ FTO, wherein the aperture of anodic oxidation aluminium formwork is about 80nm。
(6) silica gel for removing encapsulated electrode, is put into the cyanamide solution of concentration that (the cyanamide aqueous solution of 50wt% is at 50 DEG C Placed 3 days in vacuum drying oven), the ultrasound 8min, power 100w in ultrasonic cleaner.It after ultrasound, takes out, removes table Then the extra cyanamide solution in face the sheet glass of the sizes such as one piece and encases sealing with tinfoil in its surface cover, then by it It is put into ceramic crucible, then is sealed ceramic crucible with tinfoil.
(7) crucible being sealed 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, and is cooled to room temperature to temperature, closes gas, takes out sample.The sample that reaction obtains is placed in 5h is impregnated in 0.12M NaOH solution, is removed template, is obtained g-CN nanometer pipe array electrode, wherein g-CN nanotube is averaged Caliber about 80nm, length 600nm.
Embodiment 6
(1) ITO is cut into 2cm*2.5cm size, successively each ultrasound 15min in isopropanol, acetone and ethyl alcohol, Then with being dried with nitrogen.
(2) clean one end ITO is stained with high temperature gummed tape, Ti, 50nm that 10nm thickness is then successively sputtered on ITO are thick W and 750nm thickness Al, be labeled as Al/Ti/W/ITO.
(3) silica gel packaging Al/Ti/W/ITO electrode is used, 2-5 days is then stood, silica gel is allowed sufficiently to solidify.
(4) sulfuric acid of 98wt% is mixed to (wherein, the volume ratio of water and alcohol is 1:1) with water and alcohol, keeps sulfuric acid water alcohol molten The mass fraction of liquid is 5.5wt%.
(5) electrode prepared by step (3) is placed in 0.55M sulfuric acid water-alcohol solution, oxidation voltage 20V, anodic oxidation When transparent to electrode, terminate oxidation, be then immersed in 5wt%H3PO4In solution, reaming 35min obtains the sun of substrate support Pole alumina formwork is labeled as AAO-S/Ti/W/ITO, wherein the aperture of anodic oxidation aluminium formwork is about 30nm.
(6) silica gel for removing encapsulated electrode, is put into the cyanamide solution of concentration that (the cyanamide aqueous solution of 50wt% is at 50 DEG C Placed 3 days in vacuum drying oven), the ultrasound 6min, power 100w in ultrasonic cleaner.It after ultrasound, takes out, removes table Then the extra cyanamide solution in face the sheet glass of the sizes such as one piece and encases sealing with tinfoil in its surface cover, then by it It is put into ceramic crucible, then is sealed ceramic crucible with tinfoil.
(7) crucible being sealed 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, and is cooled to room temperature to temperature, closes gas, takes out sample.The sample that reaction obtains is placed in 3h is impregnated in 0.12M NaOH solution, is removed template, is obtained g-CN nanometer pipe array electrode, wherein g-CN nanotube is averaged Caliber about 30nm, length 750nm.
Embodiment 7
(1) ITO is cut into 2cm*2.5cm size, successively each ultrasound 12min in isopropanol, acetone and ethyl alcohol, Then with being dried with nitrogen.
(2) clean one end ITO is stained with high temperature gummed tape, Ti, 60nm that 8nm thickness is then successively sputtered on ITO are thick W and 1100nm thickness Al, be labeled as Al/Ti/W/ITO.
(3) silica gel packaging Al/Ti/W/ITO electrode is used, 2-5 days is then stood, silica gel is allowed sufficiently to solidify.
(4) citric acid is mixed to (wherein, the volume ratio of water and alcohol is 1:1) with water and alcohol, obtains the citric acid water of 0.15M Then the oxalic acid aqueous solution of the citric acid water alcoholic solution of 0.15M and 0.3M are mixed according to volume ratio 10:1, obtain lemon by alcoholic solution The mixed solution of lemon sour water alcoholic solution and oxalic acid aqueous solution.
(5) electrode prepared by step (3) is placed in the mixed solution of citric acid water alcoholic solution and oxalic acid aqueous solution, is aoxidized Voltage is 120V, when anodic oxidation is transparent to electrode, terminates oxidation, is then immersed in 5wt%H3PO4In solution, reaming 250min obtains the anodic oxidation aluminium formwork of substrate support, is labeled as AAO- (O+C)/Ti/W/ITO, wherein anodised aluminium The aperture of template is about 170nm.
(6) silica gel for removing encapsulated electrode, is put into the cyanamide solution of concentration that (the cyanamide aqueous solution of 50wt% is at 50 DEG C Placed 3 days in vacuum drying oven), the ultrasound 8min, power 100w in ultrasonic cleaner.It after ultrasound, takes out, removes table Then the extra cyanamide solution in face the sheet glass of the sizes such as one piece and encases sealing with tinfoil in its surface cover, then by it It is put into ceramic crucible, then is sealed ceramic crucible with tinfoil.
(7) crucible being sealed 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, and is cooled to room temperature to temperature, closes gas, takes out sample.The sample that reaction obtains is placed in 8h is impregnated in 0.12M NaOH solution, is removed template, is obtained g-CN nanometer pipe array electrode, wherein g-CN nanotube is averaged Caliber about 170nm, length 1100nm.
The Applicant declares that the present invention is explained by the above embodiments method detailed of the invention, but the present invention not office Be limited to above-mentioned method detailed, that is, do not mean that the invention must rely on the above detailed methods to implement.Technical field 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., all of which fall within the scope of protection and disclosure of the present invention.

Claims (67)

1. a kind of graphite type carbon nitride nanotube array photoelectrode, which is characterized in that the graphite type carbon nitride nano-tube array Optoelectronic pole is made of substrate and the graphite type carbon nitride nano-tube array in the substrate, the graphite type carbon nitride nanometer Pipe array is formed by graphite type carbon nitride Nanotube alignment；
The preparation method of the graphite type carbon nitride nanotube array photoelectrode the following steps are included:
(1) adhesion layer is sputtered in substrate；
(2) continue to sputter Al film, encapsulation on adhesion layer；
(3) electrode that step (2) encapsulation obtains is placed in electrolyte, carries out anodic oxidation；
(4) electrode that step (3) anodic oxidation obtains is placed in H3PO4Reaming in solution obtains the anodised aluminium of substrate support Template；
(5) removal encapsulates, and pours into cyanamide in the anodic oxidation aluminium formwork of the substrate support obtained to step (4), obtains substrate branch The template for pouring into cyanamide of support；
(6) it is sealed processing, is then annealed under inert gas protection；
(7) removing template is removed, graphite type carbon nitride nanotube array photoelectrode is obtained.
2. graphite type carbon nitride nanotube array photoelectrode according to claim 1, which is characterized in that the graphite mould nitrogen The diameter of carbon nano tube is 20nm-170nm.
3. graphite type carbon nitride nanotube array photoelectrode according to claim 2, which is characterized in that the graphite mould nitrogen The diameter of carbon nano tube is 70nm-150nm.
4. graphite type carbon nitride nanotube array photoelectrode according to claim 1, which is characterized in that the graphite mould nitrogen The length of carbon nano tube is 400nm-2500nm.
5. graphite type carbon nitride nanotube array photoelectrode according to claim 4, which is characterized in that the graphite mould nitrogen The length of carbon nano tube is 400nm-1600nm.
6. graphite type carbon nitride nanotube array photoelectrode according to claim 1, which is characterized in that the substrate is to lead Electric substrate.
7. graphite type carbon nitride nanotube array photoelectrode according to claim 6, which is characterized in that the substrate is Any one in ito glass, FTO glass or Si piece.
8. such as the preparation method of the described in any item graphite type carbon nitride nanotube array photoelectrodes of claim 1-7, feature It is, the described method comprises the following steps:
(1) adhesion layer is sputtered in substrate；
(2) continue to sputter Al film, encapsulation on adhesion layer；
(3) electrode that step (2) encapsulation obtains is placed in electrolyte, carries out anodic oxidation；
(4) electrode that step (3) anodic oxidation obtains is placed in H3PO4Reaming in solution obtains the anodised aluminium of substrate support Template；
(5) removal encapsulates, and pours into cyanamide in the anodic oxidation aluminium formwork of the substrate support obtained to step (4), obtains substrate branch The template for pouring into cyanamide of support；
(6) it is sealed processing, is then annealed under inert gas protection；
(7) removing template is removed, graphite type carbon nitride nanotube array photoelectrode is obtained.
9. according to the method described in claim 8, it is characterized in that, step (1) substrate is conductive substrates.
10. according to the method described in claim 9, it is characterized in that, step (1) substrate be ito glass, FTO glass or Any one in Si piece.
11. according to the method described in claim 8, it is characterized in that, step (1) described substrate first carries out ultrasound before the use The step of cleaning and drying.
12. according to the method described in claim 8, it is characterized in that, step (1) described adhesion layer with a thickness of 5nm-70nm.
13. according to the method described in claim 8, it is characterized in that, step (1) adhesion layer is TiO2Layer, or for by Ti The combination layer of layer and W layers of composition.
14. according to the method for claim 13, which is characterized in that step (1) adhesion layer is TiO2Layer, and it is described TiO2Layer with a thickness of 20nm-50nm.
15. according to the method for claim 14, which is characterized in that step (1) adhesion layer is the TiO of 30nm thickness2Layer.
16. according to the method for claim 13, which is characterized in that step (1) adhesion layer is to be constituted by Ti layers and W layers Combination layer, and the Ti layer in the combination layer with a thickness of 5nm-10nm, described W layers with a thickness of 40nm-70nm.
17. according to the method for claim 16, which is characterized in that step (1) adhesion layer is the Ti layer by 10nm thickness The combination layer constituted with the W layer of 60nm thickness.
18. according to the method for claim 13, which is characterized in that when step (1) adhesion layer is TiO2When layer, in step Suddenly (1) has sputtered TiO2After layer, before step (2) sputters Al film, proceed as follows: to having sputtered TiO2Layer substrate into Row annealing.
19. according to the method for claim 18, which is characterized in that having sputtered TiO2What the substrate of layer was made annealing treatment In the process, annealing temperature is 450 DEG C -550 DEG C.
20. according to the method for claim 19, which is characterized in that having sputtered TiO2What the substrate of layer was made annealing treatment In the process, annealing temperature is 500 DEG C.
21. according to the method for claim 18, which is characterized in that having sputtered TiO2What the substrate of layer was made annealing treatment In the process, annealing time 30min-4h.
22. according to the method for claim 21, which is characterized in that having sputtered TiO2What the substrate of layer was made annealing treatment In the process, annealing time 2h.
23. according to the method for claim 18, which is characterized in that having sputtered TiO2What the substrate of layer was made annealing treatment In the process, the heating rate for being warming up to annealing temperature is 10 DEG C/min-20 DEG C/min.
24. according to the method for claim 23, which is characterized in that having sputtered TiO2What the substrate of layer was made annealing treatment In the process, the heating rate for being warming up to annealing temperature is 16 DEG C/min.
25. according to the method described in claim 8, it is characterized in that, step (2) the Al film with a thickness of 400nm- 2500nm。
26. according to the method for claim 25, which is characterized in that step (2) the Al film with a thickness of 400nm- 1600nm。
27. according to the method described in claim 8, it is characterized in that, step (2) described encapsulation are as follows: using silica gel to sputtering Al Electrode after film is packaged and solidifies.
28. according to the method described in claim 8, it is characterized in that, step (3) electrolyte is that oxalic acid solution, phosphoric acid are molten In liquid, sulfuric acid solution or citric acid solution any one or at least two combination.
29. according to the method for claim 28, which is characterized in that step (3) electrolyte is oxalic acid aqueous solution, phosphoric acid Aqueous solution, the mixed solution of sulfuric acid water-alcohol solution or citric acid water alcoholic solution and oxalic acid aqueous solution.
30. according to the method for claim 29, which is characterized in that step (3) electrolyte is the oxalic acid of 0.2M-0.4M Aqueous solution, the phosphate aqueous solution of 5wt%-10wt%, the sulfuric acid water-alcohol solution or citric acid water alcoholic solution and oxalic acid of 0.5M-1M Any one in the mixed solution of aqueous solution.
31. according to the method for claim 30, which is characterized in that the sulfuric acid water-alcohol solution of the 0.5M-1M passes through as follows Method is prepared: the sulfuric acid of 98wt% being mixed with water and alcohol, makes the molar concentration 0.5M-1M of sulfuric acid water-alcohol solution.
32. according to the method for claim 31, which is characterized in that during the sulfuric acid water-alcohol solution for preparing 0.5M-1M, The volume ratio of water and alcohol is 1:1.
33. according to the method for claim 30, which is characterized in that the citric acid water alcoholic solution and oxalic acid aqueous solution it is mixed It closes solution to be prepared via a method which to obtain: citric acid being mixed with water and alcohol, obtains the citric acid water alcoholic solution of 0.15M, so The oxalic acid aqueous solution of the citric acid water alcoholic solution of 0.15M and 0.3M are mixed according to volume ratio 10:1-60:1 afterwards.
34. according to the method for claim 33, which is characterized in that prepare the mixed of citric acid water alcoholic solution and oxalic acid aqueous solution During closing solution, the volume ratio of water and alcohol is 1:1.
35. according to the method described in claim 8, it is characterized in that, voltage is during step (3) carries out anodic oxidation 10V-120V。
36. according to the method for claim 30, which is characterized in that when the electrolyte that step (3) uses is 0.2M-0.4M's When oxalic acid, during carrying out anodic oxidation, voltage 30V-60V.
37. according to the method for claim 36, which is characterized in that when the electrolyte that step (3) uses is 0.2M-0.4M's When oxalic acid, during carrying out anodic oxidation, voltage 40V.
38. according to the method for claim 30, which is characterized in that when the electrolyte that step (3) uses is 5wt%- When the phosphoric acid solution of 10wt%, during carrying out anodic oxidation, voltage 70V-100V.
39. according to the method for claim 38, which is characterized in that when the electrolyte that step (3) uses is 5wt%- When the phosphoric acid solution of 10wt%, during carrying out anodic oxidation, voltage 86V.
40. according to the method for claim 30, which is characterized in that when the sulphur that the electrolyte that step (3) uses is 0.5M-1M When sour water alcoholic solution, during carrying out anodic oxidation, voltage 10V-25V.
41. according to the method for claim 40, which is characterized in that when the sulphur that the electrolyte that step (3) uses is 0.5M-1M When sour water alcoholic solution, during carrying out anodic oxidation, voltage 20V.
42. according to the method for claim 30, which is characterized in that when the electrolyte that step (3) uses is citric acid water alcohol When the mixed solution of solution and oxalic acid aqueous solution, during carrying out anodic oxidation, voltage 90V-120V.
43. according to the method for claim 42, which is characterized in that when the electrolyte that step (3) uses is citric acid water alcohol When the mixed solution of solution and oxalic acid aqueous solution, during carrying out anodic oxidation, voltage 120V.
44. according to the method described in claim 8, it is characterized in that, step (4) described H3PO4The mass fraction of solution is 5wt%.
45. according to the method described in claim 8, it is characterized in that, the time of step (4) described reaming is 40min- 300min。
46. according to the method for claim 45, which is characterized in that the time of step (4) described reaming is 80min- 140min。
47. according to the method described in claim 8, it is characterized in that, step (5) substrate support obtained to step (4) Anodic oxidation aluminium formwork in pour into the process of cyanamide are as follows: the anodic oxidation aluminium formwork of substrate support is immersed in cyanamide solution, Ultrasound obtains the template for pouring into cyanamide of substrate support.
48. according to the method for claim 47, which is characterized in that the cyanamide solution is the cyanamide solution of concentration, described The concentration of the cyanamide solution of concentration is 75wt%-95wt%.
49. according to the method for claim 48, which is characterized in that the cyanamide solution of the concentration obtains by the following method It arrives: the cyanamide aqueous solution that mass fraction is 50wt% being placed 3 days in 50 DEG C of vacuum drying ovens, the cyanamide solution being concentrated.
50. according to the method for claim 47, which is characterized in that the time of the ultrasound is 5min-10min.
51. according to the method described in claim 8, it is characterized in that, the process of step (6) described encapsulation process are as follows: in substrate The glass for pouring into the sizes such as one piece of cover in the template of cyanamide of support, is encased with tinfoil, is then placed in crucible, then use tinfoil By sealed crucible.
52. according to the method described in claim 8, it is characterized in that, step (6) inert gas is helium, neon, argon In gas, Krypton or xenon any one or at least two gaseous mixture.
53. method according to claim 52, which is characterized in that step (6) inert gas is argon gas.
54. according to the method described in claim 8, it is characterized in that, the speed that is passed through of step (6) described inert gas is 50sccm-200sccm。
55. method according to claim 54, which is characterized in that the speed that is passed through of step (6) described inert gas is 100sccm。
56. according to the method described in claim 8, it is characterized in that, annealing temperature is during step (6) described annealing 480℃-550℃。
57. method according to claim 56, which is characterized in that during step (6) described annealing, annealing temperature is 550℃。
58. according to the method described in claim 8, it is characterized in that, annealing time is during step (6) described annealing 3h-6h。
59. method according to claim 58, which is characterized in that during step (6) described annealing, annealing time is 4h。
60. according to the method described in claim 8, it is characterized in that, step (6) is warming up to the heating rate of the annealing temperature For 2 DEG C/min-3 DEG C/min.
61. method according to claim 60, which is characterized in that step (6) is warming up to the heating speed of the annealing temperature Rate is 2.5 DEG C/min.
62. according to the method described in claim 8, it is characterized in that, step (7) process for removing removing template are as follows: by step (7) electrode after making annealing treatment immerses in NaOH solution.
63. method according to claim 62, which is characterized in that during removing removing template described in step (7), NaOH is molten The concentration of liquid is 0.12M.
64. method according to claim 62, which is characterized in that during removing removing template described in step (7), immersion Time is 3h-12h.
65. according to the method described in claim 8, it is characterized in that, the method also includes the steps (6) after step (5) It carries out before step (5) ': removing the cyanamide solution of the template surface for pouring into cyanamide of substrate support.
66. according to the method described in claim 8, it is characterized in that, the method also includes the steps (7) after step (6) Carry out before step (6) ': cooling down and closing is passed through inert gas.
67. such as the purposes of the described in any item graphite type carbon nitride nanotube array photoelectrodes of claim 1-7, feature exists In the graphite type carbon nitride nanotube array photoelectrode is used for solar energy electrochemical decomposition aquatic products oxygen as light anode.
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