CN110484957B - Preparation method of photoelectrode - Google Patents
Preparation method of photoelectrode Download PDFInfo
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- CN110484957B CN110484957B CN201910801605.3A CN201910801605A CN110484957B CN 110484957 B CN110484957 B CN 110484957B CN 201910801605 A CN201910801605 A CN 201910801605A CN 110484957 B CN110484957 B CN 110484957B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 126
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 91
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 73
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 59
- 239000002071 nanotube Substances 0.000 claims abstract description 54
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 38
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 31
- 239000010439 graphite Substances 0.000 claims abstract description 31
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 22
- 239000003792 electrolyte Substances 0.000 claims abstract description 20
- 238000000151 deposition Methods 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000006185 dispersion Substances 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 28
- 229910052719 titanium Inorganic materials 0.000 claims description 28
- 239000010936 titanium Substances 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 15
- 229910001868 water Inorganic materials 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000004070 electrodeposition Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 239000012286 potassium permanganate Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 235000010344 sodium nitrate Nutrition 0.000 claims description 6
- 239000004317 sodium nitrate Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 6
- 239000012498 ultrapure water Substances 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 239000007832 Na2SO4 Substances 0.000 claims description 2
- 230000027756 respiratory electron transport chain Effects 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 5
- 230000001699 photocatalysis Effects 0.000 abstract description 10
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 244000137852 Petrea volubilis Species 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 6
- 230000031700 light absorption Effects 0.000 description 6
- 239000011941 photocatalyst Substances 0.000 description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- 229920000877 Melamine resin Polymers 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- 238000012643 polycondensation polymerization Methods 0.000 description 4
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- 238000005286 illumination Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 2
- 229940043267 rhodamine b Drugs 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
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- 230000008021 deposition Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/26—Anodisation of refractory metals or alloys based thereon
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
- C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
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Abstract
The invention discloses a preparation method of a photoelectrode, which comprises the following steps: (1) preparing a titanium dioxide nanotube array photoelectrode; (2) depositing under voltage by taking the graphite-phase carbon nitride solution as electrolyte, the titanium dioxide nanotube array photoelectrode as a cathode and a platinum sheet as an anode to obtain the graphite-phase carbon nitride-doped titanium dioxide nanotube array photoelectrode; (3) and depositing under voltage by taking the graphene dispersion liquid as electrolyte, the titanium dioxide nanotube array photoelectrode doped with graphite phase carbon nitride as a cathode and a platinum sheet as an anode to obtain the titanium dioxide nanotube array photoelectrode doped with graphite phase carbon nitride and graphene. The titanium dioxide nanotube array photoelectrode has the advantages of good stability, high photoelectric conversion efficiency, high photocatalytic activity, greenness and no pollution.
Description
Technical Field
The invention relates to the technical field of composite photoelectrodes, in particular to a preparation method of a photoelectrode.
Background
The titanium dioxide has excellent physical and chemical stability, no toxic action, low cost, easy obtaining and good photocatalytic performance, and occupies an important position in the field of semiconductor catalysis. However, TiO2The photocatalyst also has two main drawbacks: firstly, the forbidden band width of titanium dioxide is wide (3.2eV), the titanium dioxide does not respond to visible light, only ultraviolet light with energy larger than the forbidden band width is absorbed to excite the generated photoproduction holes and electrons to carry out redox reaction on pollutants, however, the ultraviolet light in sunlight accounts for less than 5%, so that the utilization rate of the titanium dioxide to solar energy is extremely low; and secondly, the titanium dioxide absorbs photon energy to generate a high recombination rate of photogenerated holes and electrons, so that the photocatalytic activity of the titanium dioxide is severely limited. Therefore, the development of a photocatalyst having a wide light absorption range, high catalytic efficiency and good stability is a problem to be solved.
In order to solve the above problems, a lot of research has been carried out, but these technologies are either complicated to operate, expensive and costly, or the prepared photoelectrode has poor stability and low photocatalytic activity, and does not meet the requirements of environmental development and market technology. Therefore, it is very important to prepare an electrode which is cheap, has good stability, high photocatalytic activity, no pollution, high photoelectric conversion efficiency and visible light photocatalytic activity.
In view of the above, the applicant adopts the graphite phase carbon nitride and TiO with visible light response semiconductor with lower forbidden band width2The composite material is compounded and modified by graphene on the basis of semiconductor compounding, so that the corresponding range of the material to visible light is improved, the photoelectric conversion capacity of a photoelectrode is improved, and TiO is improved2The prepared photoelectrode has poor stability and low photocatalytic activity, and does not meet the requirements of environmental development and market technology.
Disclosure of Invention
The invention provides a preparation method of a photoelectrode, and aims to develop a photocatalyst which has the advantages of good stability, high photoelectric conversion efficiency, high photocatalytic activity, greenness and no pollution.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a preparation method of a photoelectrode comprises the following preparation steps:
(1) titanium sheet is used as anode, platinum sheet is used as cathode, NaF and Na are selected2SO4Placing the mixed solution as electrolyte in a water bath kettle at 15-30 ℃, oxidizing for 1-4h under the condition that the oxidation voltage is 15-25V, washing with deionized water, and drying with a blast drier to obtain a titanium dioxide nanotube array photoelectrode;
(2) placing graphite-phase carbon nitride powder in ultrapure water for 5-10h by ultrasonic treatment to prepare a graphite-phase carbon nitride solution, taking the graphite-phase carbon nitride solution as an electrolyte, taking the titanium dioxide nanotube array photoelectrode prepared in the step (1) as a cathode and a platinum sheet as an anode, and depositing for 1-10min under the condition that the voltage is 1-10V to obtain the titanium dioxide nanotube array photoelectrode doped with graphite-phase carbon nitride;
(3) and (3) placing graphite oxide in water, ultrasonically stripping for 1-3h to obtain a graphene oxide dispersion liquid, taking the graphene dispersion liquid as an electrolyte, taking the titanium dioxide nanotube array photoelectrode doped with graphite-phase carbon nitride prepared in the step (2) as a cathode, taking a platinum sheet as an anode, and depositing for 1-10min under the condition that the voltage is 1-10V to obtain the titanium dioxide nanotube array photoelectrode doped with graphite-phase carbon nitride and graphene.
Preferably, the graphene carbon nitride and the graphene are respectively loaded on the titanium dioxide nanotube array photoelectric electrode in an electrochemical deposition mode.
Preferably, the graphite-phase carbon nitride is graphene-phase carbon nitride with visible light characteristics, and the graphene is graphene with electron transfer capability.
Preferably, in the step (1), the titanium sheet is ground and polished by 600-mesh, 1000-mesh and 2000-mesh sandpaper in sequence before use.
Preferably, the titanium sheet in the step (1) is a strip sheet with the specification of 80mm × 10mm × 0.2mm, and the platinum sheet is a strip sheet with the same size as the titanium sheet.
Preferably, the concentration of NaF in the step (1) is 0.2 to 0.6 wt%, Na2SO4The concentration is 0.5-1.5 mol/L.
Preferably, the concentration of the graphite-phase carbon nitride solution in the step (2) is 30-100 mg/L.
Preferably, the preparation method of graphite oxide in the step (3) comprises the following steps: graphite powder is used as a raw material to prepare water-soluble graphene oxide, the graphite powder and sodium nitrate are mixed according to the mass ratio of 1:0.5 and then added into concentrated sulfuric acid, the mixture is stirred in an ice bath, potassium permanganate solid with the mass 3-4 times that of the graphite powder is slowly added after 30min, the reaction temperature is guaranteed to be lower than 10 ℃, the mixture is continuously stirred for 8-10H, and then H is added2Slowly adding O, stirring at 98 deg.C for 20-24 hr, adding 30% H2O2Stirring uniformly, then washing with 5% HCl and deionized water, and centrifugally filtering to obtain graphite oxide.
Compared with the prior art, the invention has the following beneficial effects:
(1) graphite phase carbon nitride reduced TiO2Band gap value of TiO2The photoresponse range of the compound is widened to a visible light region, sunlight can be more efficiently utilized, and meanwhile TiO2The energy level of the carbon nitride is matched with that of the graphite phase carbon nitride, the carbon nitride and the graphite phase carbon nitride can form a heterojunction during illumination, and simultaneously, a photon-generated carrier is effectively separated, so that the method is an effective method for widening the light absorption range of the heterojunction and promoting charge separation;
(2) TiO adopted in the invention2Has higher specific surface area and abundant active sites, the introduction of the graphene further increases the specific surface area of the photocatalyst, improves the photoelectric conversion capability of the photoelectrode, and TiO2The photoproduction electron hole reversely flows under the action of the built-in potential of the heterostructure, and the separation efficiency of the electron and the hole is improved;
(3) compared with the traditional method that the graphite phase carbon nitride solution is dipped by a brush and coated on the titanium dioxide nanotube array photoelectrode, the method adopts the electrochemical deposition method, so that the graphite phase carbon nitride can be more uniformly distributed on the titanium dioxide nanotube array photoelectrode, meanwhile, the loading process and the doping amount of the carbon nitride are convenient and controllable, the adhesion between the deposited carbon nitride and the nanotubes is strong, the combination is firmer, the obtained composite electrode is stable, and the improvement of the photocatalysis performance of the photoelectrode is facilitated;
(4) the titanium dioxide nanotube array photoelectrode is green and pollution-free, and meanwhile, the preparation condition is mild, simple, convenient and reliable.
Drawings
FIG. 1 is a HRTEM image of a photoelectrode prepared in example 1 of the present invention;
FIG. 2 is an XPS fine scan of a photoelectrode prepared in example 2 of the present invention (with the abscissa representing average binding energy and the ordinate representing intensity);
FIG. 3 is an XPS survey of a photoelectrode prepared in example 3 of the present invention (with the abscissa representing average binding energy and the ordinate representing intensity);
FIG. 4 is a graph showing the degradation rate of rhodamine B in the photoelectrode prepared in example 4 of the present invention and the photoelectrodes prepared in comparative examples 1 and 2;
fig. 5 shows the light absorption properties (wavelength on the abscissa and absorbance on the ordinate) of the photoelectrode produced in example 4 of the present invention and those produced in comparative examples 1 and 2.
Detailed Description
The following detailed description of the preferred embodiments of the present invention, taken in conjunction with the accompanying drawings, will make the advantages and features of the invention easier to understand by those skilled in the art, and thus will clearly and clearly define the scope of the invention.
The preparation method of the photoelectrode shown in figures 1, 2, 3 and 4 is characterized by comprising the following steps:
example 1
The preparation method of the photoelectrode of the embodiment comprises the following steps:
(1) pretreating a titanium sheet, wherein the titanium sheet is a strip-shaped sheet with the specification of 80mm × 10mm × 0.2.2 mm, the titanium content in the titanium sheet is more than 99.9%, sequentially selecting 600-mesh sand paper, 1000-mesh sand paper and 2000-mesh sand paper for grinding and polishing, taking the pretreated titanium sheet as an anode, taking a platinum sheet with the same size as a cathode, and taking 0.5 wt% of NaF and 1.0mol/LNa as electrolytes2SO4Oxidizing the formed 100mL mixed solution for 2h in a water bath at 20 ℃ under the condition that the oxidation voltage is 20V, washing with deionized water, and drying with a blast drier to obtain a titanium dioxide nanotube array photoelectrode;
(2) preparing carbon nitride powder by adopting a melamine thermal condensation polymerization method, dissolving a certain amount of carbon nitride powder in ultrapure water, performing ultrasonic treatment for 8 hours to prepare a carbon nitride solution with the concentration of 50mg/L, modifying a titanium dioxide nanotube array photoelectrode by adopting a graphite-phase carbon nitride method by adopting an electrochemical deposition method, taking the carbon nitride solution (50mg/L) as an electrolyte, taking the titanium dioxide nanotube array photoelectrode prepared in the step (1) as a cathode, taking a platinum sheet as an anode, and performing deposition for 10 minutes under the condition that the voltage is 1V to obtain the titanium dioxide nanotube array photoelectrode doped with the graphite-phase carbon nitride;
(3) preparing Graphite Oxide (GO) by adopting an improved Hummers method, and taking a certain amount of GO to ultrasonically strip in water for 1h to obtain oxidized graphiteAnd (2) modifying the graphite-phase carbon nitride-doped titanium dioxide nanotube array photoelectrode by using graphene through a graphene dispersion liquid (20mg/L), taking the GO dispersion liquid (20mg/L) as an electrolyte, taking the graphite-phase carbon nitride-doped titanium dioxide nanotube array photoelectrode prepared in the step (2) as a cathode, taking a platinum sheet as an anode, and depositing for 5min under the condition that the voltage is 2V, thereby obtaining the graphite-phase carbon nitride and graphene-doped titanium dioxide nanotube array photoelectrode (namely rGO/g-C) through an electrochemical deposition method3N4/TNAs)。
Wherein the preparation method of the graphite oxide in the step (3) comprises the following steps: graphite powder is used as a raw material to prepare water-soluble graphene oxide, the graphite powder and sodium nitrate are mixed according to the mass ratio of 1:0.5 and then added into concentrated sulfuric acid, the mixture is stirred in an ice bath, potassium permanganate solid with the mass 3 times that of the graphite powder is slowly added after 30min, the reaction temperature is guaranteed to be lower than 10 ℃, the mixture is continuously stirred for 8H, and then H is added2Slowly adding O, stirring at 98 deg.C for 20 hr, adding 30% H2O2Stirring uniformly, then washing with 5% HCl and deionized water, and centrifugally filtering to obtain graphite oxide.
Example 2:
the preparation method of the photoelectrode of the embodiment comprises the following steps:
(1) pretreating a titanium sheet, wherein the titanium sheet is a strip-shaped sheet with the specification of 80mm × 10mm × 0.2.2 mm, the titanium content in the titanium sheet is more than 99.9%, sequentially selecting 600-mesh sand paper, 1000-mesh sand paper and 2000-mesh sand paper for grinding and polishing, taking the pretreated titanium sheet as an anode, taking a platinum sheet with the same size as a cathode, and taking 0.5 wt% of NaF and 1.0mol/LNa as electrolytes2SO4Oxidizing the formed 100mL mixed solution for 2h in a water bath at 20 ℃ under the condition that the oxidation voltage is 20V, washing with deionized water, and drying with a blast drier to obtain a titanium dioxide nanotube array photoelectrode;
(2) preparing carbon nitride powder by adopting a melamine thermal condensation polymerization method, dissolving a certain amount of carbon nitride powder in ultrapure water, performing ultrasonic treatment for 7 hours to prepare a carbon nitride solution with the concentration of 50mg/L, modifying a titanium dioxide nanotube array photoelectrode by adopting a graphite-phase carbon nitride method by adopting an electrochemical deposition method, taking the carbon nitride solution (50mg/L) as an electrolyte, taking the titanium dioxide nanotube array photoelectrode prepared in the step (2) as a cathode, taking a platinum sheet as an anode, and depositing for 10 minutes under the condition of the voltage of 2V to obtain the titanium dioxide nanotube array photoelectrode doped with the graphite-phase carbon nitride;
(3) preparing Graphite Oxide (GO) by adopting an improved Hummers method, ultrasonically stripping a certain amount of GO in water for 3 hours to obtain graphene oxide dispersion liquid (20mg/L), then modifying a titanium dioxide nanotube array photoelectrode doped with graphite-phase carbon nitride by using graphene by adopting an electrochemical deposition method, taking the GO dispersion liquid (20mg/L) as electrolyte, taking the titanium dioxide nanotube array photoelectrode doped with graphite-phase carbon nitride prepared in the step (2) as a cathode, taking a platinum sheet as an anode, and depositing for 5 minutes under the condition that the voltage is 2V, thereby obtaining the titanium dioxide nanotube array photoelectrode doped with graphite-phase carbon nitride and graphene (namely rGO/g-C GO)3N4/TNAs)。
Wherein, the preparation method of the graphite oxide in the step (3) comprises the following steps: graphite powder is used as a raw material to prepare water-soluble graphene oxide, the graphite powder and sodium nitrate are mixed according to the mass ratio of 1:0.5 and then added into concentrated sulfuric acid, the mixture is stirred in an ice bath, potassium permanganate solid with the mass 4 times that of the graphite powder is slowly added after 30min, the reaction temperature is guaranteed to be lower than 10 ℃, the mixture is continuously stirred for 10H, and then H is added2Slowly adding O, stirring at 98 deg.C for 24 hr, adding 30% H2O2Stirring uniformly, then washing with 5% HCl and deionized water, and centrifugally filtering to obtain graphite oxide.
Example 3:
the preparation method of the photoelectrode of the embodiment comprises the following steps:
(1) pretreating a titanium sheet, wherein the titanium sheet is a strip-shaped sheet with the specification of 80mm × 10mm × 0.2.2 mm, the titanium content in the titanium sheet is more than 99.9%, sequentially selecting 600-mesh sand paper, 1000-mesh sand paper and 2000-mesh sand paper for grinding and polishing, taking the pretreated titanium sheet as an anode, taking a platinum sheet with the same size as a cathode, and taking 0.5 wt% of NaF and 1.0mol/LNa as electrolytes2SO4100mL of the mixed solution is put in a water bath at 20 DEG CIn a pot, under the condition that the oxidation voltage is 20V, after oxidizing for 2h, washing with deionized water, and drying with a blast drier to obtain a titanium dioxide nanotube array photoelectrode;
(3) preparing carbon nitride powder by adopting a melamine thermal condensation polymerization method, dissolving a certain amount of carbon nitride powder in ultrapure water, performing ultrasonic treatment for 7 hours to prepare a carbon nitride solution with the concentration of 50mg/L, modifying a titanium dioxide nanotube array photoelectrode by adopting a graphite-phase carbon nitride method by adopting an electrochemical deposition method, taking the carbon nitride solution (50mg/L) as an electrolyte, taking the titanium dioxide nanotube array photoelectrode prepared in the step (1) as a cathode, taking a platinum sheet as an anode, and depositing for 10min under the condition of the voltage of 3V to obtain the titanium dioxide nanotube array photoelectrode doped with the graphite-phase carbon nitride;
(3) preparing Graphite Oxide (GO) by adopting an improved Hummers method, ultrasonically stripping a certain amount of GO in water for 2 hours to obtain graphene oxide dispersion liquid (20mg/L), then modifying a titanium dioxide nanotube array photoelectrode doped with graphite-phase carbon nitride by using graphene by adopting an electrochemical deposition method, using the GO dispersion liquid (20mg/L) as electrolyte, using the annealed titanium dioxide nanotube array photoelectrode doped with graphite-phase carbon nitride as a cathode, using a platinum sheet as an anode, and depositing for 5 minutes under the condition that the voltage is 2V, thereby obtaining the titanium dioxide nanotube array photoelectrode doped with graphite-phase carbon nitride and graphene (namely rGO/g-C)3N4/TNAs)。
Wherein, the preparation method of the graphite oxide in the step (3) comprises the following steps: graphite powder is used as a raw material to prepare water-soluble graphene oxide, the graphite powder and sodium nitrate are mixed according to the mass ratio of 1:0.5 and then added into concentrated sulfuric acid, the mixture is stirred in an ice bath, potassium permanganate solid with the mass 3.5 times that of the graphite powder is slowly added after 30min, the reaction temperature is guaranteed to be lower than 10 ℃, the mixture is continuously stirred for 9H, and then H is added2Slowly adding O, stirring at 98 deg.C for 22 hr, adding 30% H2O2Stirring uniformly, then washing with 5% HCl and deionized water, and centrifugally filtering to obtain graphite oxide.
Example 4:
the preparation method of the photoelectrode of the embodiment comprises the following steps:
(1) pretreating a titanium sheet, wherein the titanium sheet is a strip-shaped sheet with the specification of 80mm × 10mm × 0.2.2 mm, the titanium content in the titanium sheet is more than 99.9%, sequentially selecting 600-mesh sand paper, 1000-mesh sand paper and 2000-mesh sand paper for grinding and polishing, taking the pretreated titanium sheet as an anode, taking a platinum sheet with the same size as a cathode, and taking 0.5 wt% of NaF and 1.0mol/LNa as electrolytes2SO4Oxidizing the formed 100mL mixed solution for 2h in a water bath at 20 ℃ under the condition that the oxidation voltage is 20V, washing with deionized water, and drying with a blast drier to obtain a titanium dioxide nanotube array photoelectrode;
(2) preparing carbon nitride powder by adopting a melamine thermal condensation polymerization method, dissolving a certain amount of carbon nitride powder in ultrapure water, performing ultrasonic treatment for 7 hours to prepare a carbon nitride solution with the concentration of 50mg/L, and modifying a titanium dioxide nanotube array photoelectrode by adopting a graphite phase carbon nitride through an electrochemical deposition method. Using a carbon nitride solution (50mg/L) as an electrolyte, using the titanium dioxide nanotube array photoelectrode prepared in the step (1) as a cathode, using a platinum sheet as an anode, and depositing for 10min under the condition of a voltage of 4V to obtain the graphite-phase carbon nitride-doped titanium dioxide nanotube array photoelectrode (namely rGO/g-C)3N4/TNAs)；
(3) Preparing Graphite Oxide (GO) by adopting an improved Hummers method, ultrasonically stripping a certain amount of GO in water for 3 hours to obtain graphene oxide dispersion liquid (20mg/L), then modifying a titanium dioxide nanotube array photoelectrode doped with graphite-phase carbon nitride by using graphene by adopting an electrochemical deposition method, taking the GO dispersion liquid (20mg/L) as electrolyte, taking the titanium dioxide nanotube array photoelectrode doped with graphite-phase carbon nitride prepared in the step (2) as a cathode, taking a platinum sheet as an anode, and depositing for 5 minutes under the condition that the voltage is 2V, thereby obtaining the titanium dioxide nanotube array photoelectrode doped with graphite-phase carbon nitride and graphene.
Wherein, the preparation method of the graphite oxide in the step (3) comprises the following steps: graphite powder is used as a raw material to prepare water-soluble graphene oxide, the graphite powder and sodium nitrate are mixed according to the mass ratio of 1:0.5, then the mixture is added into concentrated sulfuric acid, the mixture is stirred in an ice bath, potassium permanganate solid with the mass 3 times that of the graphite powder is slowly added after 30min, the reaction temperature is guaranteed to be lower than 10 ℃, H2O is slowly added after continuous stirring is carried out for 8H, the mixture is continuously stirred for 23H at 98 ℃, 30% H2O2 is added and stirred uniformly, and then 5% HCl and deionized water are used for cleaning, and centrifugal filtration is carried out to obtain graphite oxide.
Comparative example 1:
except that the graphite phase carbon nitride and graphene doped titanium dioxide nanotube array photoelectrode was omitted, the steps and methods were the same as in example 4 to produce photoelectrodes (i.e., TNAs).
Comparative example 2:
except that the graphene-doped titanium dioxide nanotube array photoelectrode was omitted, the other steps and methods were the same as those of example 4, and a photoelectrode (i.e., g-C) was prepared3N4/TNAs)。
The photoelectrode prepared in example 4 and the photoelectrodes prepared in comparative examples 1 and 2 were tested for the effect of degrading rhodamine B, and the specific results are shown in fig. 4.
In addition, the photoelectrode obtained in example 4 and the photoelectrodes obtained in comparative examples 1 and 2 were subjected to light absorption tests, and the effects on light absorption were respectively tested, and the specific results are shown in fig. 5.
Therefore, the titanium dioxide nanotube array photoelectrode doped with graphite-phase carbon nitride and graphene prepared in the embodiment of the invention has stable performance, greatly improves the quantum efficiency and photoelectric conversion capability of the titanium dioxide nanotube array photoelectrode, has visible light photocatalytic activity, and can utilize most visible light energy in sunlight.
In summary, the graphite phase carbon nitride of the present invention reduces TiO2Band gap value of TiO2The photoresponse range of the compound is widened to a visible light region, sunlight can be more efficiently utilized, and meanwhile TiO2The energy level of the carbon nitride is matched with that of the graphite phase carbon nitride, the carbon nitride and the graphite phase carbon nitride can form a heterojunction during illumination, and simultaneously, a photon-generated carrier is effectively separated, so that the method is an effective method for widening the light absorption range of the heterojunction and promoting charge separation; and by adopting TiO with higher specific surface area and abundant active sites2The introduction of the graphene further increases the specific surface area of the photocatalyst, improves the photoelectric conversion capability of the photoelectrode, and the TiO further increases the specific surface area of the photocatalyst2The photoproduction electron hole reversely flows under the action of the built-in potential of the heterostructure, the separation efficiency of the electron and the hole is improved, and the preparation condition is mild, simple, convenient and reliable.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. The preparation method of the photoelectrode is characterized by comprising the following preparation steps of:
(1) titanium sheet is used as anode, platinum sheet is used as cathode, NaF and Na are selected2SO4Placing the mixed solution as electrolyte in a water bath kettle at 15-30 ℃, oxidizing for 1-4h under the condition that the oxidation voltage is 15-25V, washing with deionized water, and drying with a blast drier to obtain a titanium dioxide nanotube array photoelectrode;
(2) placing graphite-phase carbon nitride powder in ultrapure water for 5-10h by ultrasonic treatment to prepare a graphite-phase carbon nitride solution, taking the graphite-phase carbon nitride solution as an electrolyte, taking the titanium dioxide nanotube array photoelectrode prepared in the step (1) as a cathode and a platinum sheet as an anode, and depositing for 1-10min under the condition that the voltage is 1-10V to obtain the titanium dioxide nanotube array photoelectrode doped with graphite-phase carbon nitride;
(3) and (3) placing graphite oxide in water, ultrasonically stripping for 1-3h to obtain a graphene oxide dispersion liquid, taking the graphene dispersion liquid as an electrolyte, taking the titanium dioxide nanotube array photoelectrode doped with graphite-phase carbon nitride prepared in the step (2) as a cathode, taking a platinum sheet as an anode, and depositing for 1-10min under the condition that the voltage is 1-10V to obtain the titanium dioxide nanotube array photoelectrode doped with graphite-phase carbon nitride and graphene.
2. The method for preparing the photoelectrode of claim 1, wherein the graphene carbon nitride and the graphene are respectively loaded on the titanium dioxide nanotube array photoelectrode by means of electrochemical deposition.
3. The method for preparing the photoelectrode of claim 1, wherein the graphite-phase carbon nitride is graphene-phase carbon nitride having visible light characteristics, and the graphene is graphene having an electron transfer capability.
4. The method for manufacturing a photoelectrode of claim 1 wherein in step (1) the titanium sheet is sanded and polished with 600 mesh, 1000 mesh and 2000 mesh sandpaper in sequence before use.
5. The method for preparing the photoelectrode of claim 1, wherein the titanium sheet in the step (1) is a strip sheet with the specification of 80mm x 10mm x 0.2mm, and the platinum sheet is a strip sheet with the same size as the titanium sheet.
6. The method for producing a photoelectrode according to claim 1, wherein the concentration of NaF in the step (1) is 0.2 to 0.6 wt%, Na2SO4The concentration is 0.5-1.5 mol/L.
7. The method for producing a photoelectrode according to claim 1, wherein the concentration of the graphite-phase carbon nitride solution in the step (2) is 30 to 100 mg/L.
8. The method for producing a photoelectrode according to claim 1, wherein the method for producing graphite oxide in the step (3): graphite powder is used as a raw material to prepare water-soluble graphene oxide, the graphite powder and sodium nitrate are mixed according to the mass ratio of 1:0.5 and then added into concentrated sulfuric acid, the mixture is stirred in an ice bath, and after 30min, 3-Slowly adding potassium permanganate solid with the mass 4 times that of graphite powder, ensuring that the reaction temperature is lower than 10 ℃, continuously stirring for 8-10H, and then adding H2Slowly adding O, stirring at 98 deg.C for 20-24 hr, adding 30% H2O2Stirring uniformly, then washing with 5% HCl and deionized water, and centrifugally filtering to obtain graphite oxide.
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