CN110528047B - Preparation method of composite photoelectrode - Google Patents
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- CN110528047B CN110528047B CN201910801142.0A CN201910801142A CN110528047B CN 110528047 B CN110528047 B CN 110528047B CN 201910801142 A CN201910801142 A CN 201910801142A CN 110528047 B CN110528047 B CN 110528047B
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- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 143
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- 239000004408 titanium dioxide Substances 0.000 claims abstract description 67
- 239000002071 nanotube Substances 0.000 claims abstract description 58
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 40
- 239000010439 graphite Substances 0.000 claims abstract description 40
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- 238000011068 loading method Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 28
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 28
- 229910052719 titanium Inorganic materials 0.000 claims description 28
- 239000010936 titanium Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 15
- 229910001868 water Inorganic materials 0.000 claims description 15
- 229910052697 platinum Inorganic materials 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 12
- 239000007788 liquid 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
- 239000000203 mixture Substances 0.000 claims description 11
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- 239000000843 powder Substances 0.000 claims description 10
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 238000000137 annealing Methods 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 6
- 238000004070 electrodeposition 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
- 239000011734 sodium Substances 0.000 claims description 4
- 230000027756 respiratory electron transport chain Effects 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000004065 semiconductor Substances 0.000 abstract description 7
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- 230000001699 photocatalysis Effects 0.000 description 10
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
- 238000005498 polishing Methods 0.000 description 5
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- 230000000052 comparative effect Effects 0.000 description 4
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- 238000012643 polycondensation polymerization Methods 0.000 description 4
- 239000007832 Na2SO4 Substances 0.000 description 3
- 244000137852 Petrea volubilis Species 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- 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
- 238000000926 separation method Methods 0.000 description 2
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J35/33—Electric or magnetic 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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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 composite photoelectrode, which is prepared by loading graphite-phase carbon nitride and graphene on the surface of a titanium dioxide nanotube array photoelectrode, and the preparation method comprises the following steps: (1) preparing a titanium dioxide nanotube array photoelectrode; (2) preparing a titanium dioxide nanotube array photoelectrode doped with graphite phase carbon nitride; (3) and (3) preparing the graphite-phase carbon nitride-doped and graphene titanium dioxide nanotube array photoelectrode. The graphite phase carbon nitride semiconductor adopted by the invention has narrow band gap, can absorb visible light, and is TiO2The graphene has a high specific surface area, is rapid in electronic conduction capability, and can greatly improve the photoelectric conversion capability of the photoelectrode by loading.
Description
Technical Field
The invention relates to the technical field of composite photoelectrodes, in particular to a preparation method of a composite photoelectrode.
Background
The photocatalysis technology utilizes the characteristic that a semiconductor material is activated under the condition of light irradiation, can be used for catalyzing and decomposing water to produce hydrogen, reducing CO2 to prepare hydrocarbon fuel, degrading various pollutants in water and air and the like, has the advantages of mild condition, energy conservation, high efficiency and the like, thereby becoming one of effective ways for solving the current environmental pollution and energy crisis, and having important practical significance, wherein TiO2The photocatalyst has excellent physical and chemical stability, no toxic effect, 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. Thus, widening TiO2Is TiO and promotes the separation of photogenerated holes and electrons to improve the visible light utilization rate and the quantum efficiency of the material2The research difficulty in the field of photocatalysis urgently needs extensive scientific research personnel.
In order to overcome the defects, a great deal of research is carried out, but the technologies are either complex to operate, expensive and high in cost, or the prepared photoelectrode is poor in stability and low in 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 this, the applicant responded to the visible light by using a semiconductor g-C having a low forbidden band width3N4With TiO2The 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
Aiming at the defects in the prior art, the invention provides a preparation method of a composite photoelectrode, which has the advantages of mild preparation conditions, simplicity, convenience and reliability.
In order to achieve the purpose, the invention is realized by the following technical scheme:
the titanium dioxide composite photoelectrode is prepared by loading graphite-phase carbon nitride and graphene on the surface of a titanium dioxide nanotube array photoelectrode, and the outermost layer of the titanium dioxide composite photoelectrode is graphene.
Preferably, the graphene carbon nitride is loaded on the titanium dioxide composite photoelectric electrode in a coating manner, and the graphene is loaded on the titanium dioxide composite photoelectric electrode in an electrochemical deposition manner.
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, the present invention provides a method for preparing the composite photoelectrode, comprising the steps of:
(1) preparing a titanium dioxide nanotube array photoelectrode: 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) preparing a titanium dioxide nanotube array photoelectrode doped with graphite phase carbon nitride, namely placing carbon nitride powder in ultrapure water for 5-10h by ultrasonic treatment to prepare a carbon nitride solution, coating the carbon nitride solution on the titanium dioxide nanotube array photoelectrode, repeating the process for 3-5 times, placing the titanium dioxide nanotube array photoelectrode in a drying oven at 100 ℃ for drying for 30min, and then placing the titanium dioxide nanotube array photoelectrode in a muffle furnace for annealing at 300-800 ℃ for 1-3h to obtain the titanium dioxide nanotube array photoelectrode doped with graphite phase carbon nitride;
(3) the preparation method of the graphene-doped carbon nitride and graphene titanium dioxide nanotube array photoelectrode comprises the steps of placing graphite oxide in water, ultrasonically stripping for 1-3 hours to obtain graphene oxide dispersion liquid, taking the graphene dispersion liquid as electrolyte, taking the annealed and graphite-doped titanium dioxide nanotube array photoelectrode 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 composite photoelectrode.
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 said step (1) is 0.2-0.6 wt%, Na2SO4The concentration is 0.5-1.5 mol/L.
Preferably, the method of coating in the step (2): and (3) dipping the carbon nitride solution by using a brush to coat and load the prepared titanium dioxide nanotube array photoelectrode.
Preferably, the preparation method of graphite oxide in the step (3) comprises: graphite powder is used as a raw material to prepare water-soluble graphite 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:
the graphite-phase carbon nitride semiconductor adopted by the invention has a narrow band gap, can absorb visible light, and the energy levels of TiO2 and graphite-phase carbon nitride are matched, so that heterojunction can be formed during illumination, and photo-generated carriers can be effectively separated, so that the method is an effective method for widening the light absorption range of the latter and promoting charge separation, and the graphene has a high specific surface area, high electronic conductivity, good conductivity, light transmittance and chemical stability, and the load can greatly improve the photoelectric conversion capability of a photoelectrode, so that the method is green and pollution-free, and is mild in preparation conditions, simple, convenient and reliable;
in addition, the graphite-phase carbon nitride used in the invention is quantum dots, the graphene is a sheet-shaped structure, and the graphene can coat small-particle carbon nitride quantum dots and titanium dioxide nanotubes, so that the graphene can be used as a channel for transmitting electrons, the transfer of charges can be promoted, the recombination of photon-generated carriers can be inhibited, and the photocatalytic activity can be further improved.
Drawings
FIG. 1 is an XPS plot of a composite photoelectrode prepared in example 1 of the present invention (with the abscissa representing average binding energy and the ordinate representing intensity);
FIG. 2 is a HRTEM image of the composite photoelectrode prepared in example 2 of the present invention;
FIG. 3 is the light absorption properties (wavelength on the abscissa and absorbance on the ordinate) of the composite photoelectrode prepared in example 3 of the present invention;
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.
Detailed Description
The preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings so that the advantages and features of the invention may be more readily understood by those skilled in the art, and the scope of the invention will be more clearly and clearly defined
The preparation method of the composite photoelectrode shown in figures 1, 2, 3 and 4 is characterized by comprising the following steps:
example 1
The preparation method of the composite photoelectrode of the embodiment comprises the following steps:
(1) preparing a titanium dioxide nanotube array photoelectrode: pretreating a titanium sheet, wherein the titanium sheet is a strip-shaped sheet with the specification of 80mm multiplied by 10mm multiplied by 0.2mm, the content of titanium in the titanium sheet is more than 99.9 percent, 600-mesh, 1000-mesh and 2000-mesh abrasive paper are sequentially selected for grinding and polishing, the pretreated titanium sheet is taken as an anode, a platinum sheet with the same size is taken as a cathode, and the electrolyte is 0.5wt percent NaF and 1.0mol/L Na2SO4Oxidizing 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) doped graphite phasePreparing carbon nitride titanium dioxide nanotube array photoelectrode by adopting a melamine thermal condensation polymerization method to prepare carbon nitride powder, 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 dipping the prepared TiO with a brush in the carbon nitride solution2Coating and loading the nanotube array photoelectrode, repeating for 4 times, drying in an oven at 100 ℃ for 30min, and annealing in a muffle furnace at 400 ℃ for 2h to obtain the titanium dioxide nanotube array photoelectrode doped with 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 1h to obtain graphene oxide dispersion liquid (20mg/L), then adopting an electrochemical deposition method to modify the graphene-phase carbon nitride-doped titanium dioxide nanotube array photoelectrode by using graphene, using the GO dispersion liquid (20mg/L) as electrolyte, using the annealed graphite-phase carbon nitride-doped titanium dioxide nanotube array photoelectrode as a cathode, using a platinum sheet as an anode, and depositing for 5min under the condition that the voltage is 2V to obtain the composite photoelectrode (namely rGO/g-C), wherein3N4/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 graphite 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 composite photoelectrode of the embodiment comprises the following steps:
(1) preparing a titanium dioxide nanotube array photoelectrode: pretreating a titanium sheet, wherein the titanium sheet is a strip sheet with the specification of 80mm multiplied by 10mm multiplied by 0.2mm, and the titanium content in the titanium sheet is more than 99.9 percentSequentially 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/L of Na 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, dipping the carbon nitride solution by using a brush to coat and load the prepared TiO2 nanotube array photoelectrode, repeating the steps for 4 times, drying the photoelectrode in a drying oven at 100 ℃ for 30min, and then annealing the photoelectrode in a muffle furnace at 450 ℃ for 2 hours to obtain the titanium dioxide nanotube array photoelectrode doped with the graphite phase carbon nitride;
(3) preparing a 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), and then modifying the graphite-phase carbon nitride-doped titanium dioxide nanotube array photoelectrode by using graphene by adopting an electrochemical deposition method. Using GO dispersion liquid (20mg/L) as electrolyte, titanium dioxide nanotube array photoelectrode of annealed and doped graphite phase carbon nitride as cathode, platinum sheet as anode, and depositing for 5min under the condition of 2V voltage to obtain composite photoelectrode (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 graphite 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 composite photoelectrode of the embodiment comprises the following steps:
(1) preparing a titanium dioxide nanotube array photoelectrode: pretreating a titanium sheet, wherein the titanium sheet is a strip-shaped sheet with the specification of 80mm multiplied by 10mm multiplied by 0.2mm, the titanium content in the titanium sheet is more than 99.9 percent, 600 meshes, 1000 meshes and 2000 meshes of abrasive paper are sequentially selected for grinding and polishing, the pretreated titanium sheet is taken as an anode, a platinum sheet with the same size is taken as a cathode, and the electrolyte is 0.5wt percent NaF and 1.0mol/LNa2SO4Oxidizing 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;
(3) preparing a titanium dioxide nanotube array photoelectrode doped with graphite-phase carbon nitride, namely 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 dipping the prepared TiO with a brush in the carbon nitride solution2Coating and loading the nanotube array photoelectrode, repeating for 4 times, drying in an oven at 100 ℃ for 30min, and annealing in a muffle furnace at 500 ℃ for 2h to obtain the titanium dioxide nanotube array photoelectrode doped with graphite phase carbon nitride;
(3) preparing a 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), and then modifying the graphite-phase carbon nitride-doped titanium dioxide nanotube array photoelectrode by using graphene by adopting an electrochemical deposition method. Using GO dispersion liquid (20mg/L) as electrolyte, titanium dioxide nanotube array photoelectrode of annealed and doped graphite phase carbon nitride as cathode, platinum sheet as anode, and depositing for 5min under the condition of 2V voltage, thereby obtaining the composite photoelectrode (namely rGO/g-C3N4/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 graphite 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 composite photoelectrode of the embodiment comprises the following steps:
(1) preparing a titanium dioxide nanotube array photoelectrode: the method comprises the following steps of pretreating a titanium sheet, wherein the titanium sheet is a strip-shaped sheet with the specification of 80mm multiplied by 10mm multiplied by 0.2mm, the titanium content in the titanium sheet is more than 99.9%, and 600-mesh, 1000-mesh and 2000-mesh abrasive papers are selected for polishing and polishing in sequence. The pretreated titanium sheet is used as an anode, a platinum sheet with the same size is used as a cathode, and the electrolyte is 0.5 wt% of NaF and 1.0mol/L of Na2SO4Oxidizing 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 a titanium dioxide nanotube array photoelectrode doped with graphite-phase carbon nitride, namely 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 dipping the prepared TiO with a brush in the carbon nitride solution2Coating and loading the nanotube array photoelectrode, repeating for 4 times, drying in an oven at 100 ℃ for 30min, and annealing in a muffle furnace at 550 ℃ for 2h to obtain the titanium dioxide nanotube array photoelectrode doped with graphite phase carbon nitride;
(3) preparing a graphite-phase carbon nitride and graphene-doped titanium dioxide nanotube array photoelectrode by adopting an improved Hummers methodPreparing Graphite Oxide (GO), taking a certain amount of GO to ultrasonically strip in water for 3 hours to obtain graphene oxide dispersion liquid (20mg/L), and then modifying the titanium dioxide nanotube array photoelectrode doped with graphite-phase carbon nitride by using graphene by adopting an electrochemical deposition method. Using GO dispersion liquid (20mg/L) as electrolyte, titanium dioxide nanotube array photoelectrode of annealed and doped graphite phase carbon nitride as cathode, platinum sheet as anode, and depositing for 5min under the condition of 2V voltage to obtain composite photoelectrode (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 graphite 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 ℃, H2O is slowly added after stirring is continued for 8H, stirring is continued 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 to obtain the 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 steps and methods were the same as in example 4, and a photoelectrode (i.e., g-C3N4/TNAs) was prepared.
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.
Therefore, the composite photoelectrode prepared in the embodiments 1 to 4 of the invention has stable performance, greatly improves the quantum efficiency and the 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 conclusion, the graphite phase nitrogen adopted by the inventionCarbon-doped semiconductor with narrow band gap and TiO capable of absorbing visible light2The graphene has the advantages of high specific surface area, high electronic conductivity, good conductivity, light transmission and chemical stability, and the load can greatly improve the photoelectric conversion capability of the photoelectrode.
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 (6)
1. The preparation method of the composite photoelectrode is characterized in that the titanium dioxide composite photoelectrode is prepared by loading graphite-phase carbon nitride and graphene on the surface of a titanium dioxide nanotube array photoelectrode, and the outermost layer of the titanium dioxide composite photoelectrode is graphene;
the graphene carbon nitride is loaded on the titanium dioxide composite photoelectric electrode in a coating mode, and the graphene is loaded on the titanium dioxide composite photoelectric electrode in an electrochemical deposition mode;
the graphene-phase carbon nitride with visible light characteristics is selected as the graphite-phase carbon nitride, and the graphene with electron transfer capability is selected as the graphene;
the preparation method of the composite photoelectrode is characterized by comprising the following steps:
(1) preparing a titanium dioxide nanotube array photoelectrode: titanium sheet is used as anode, platinum sheet is used as cathode, NaF and Na are selected2SO4The mixed solution is used as electrolyte, placed in a water bath at 15-30 deg.C, and oxidized at oxidation voltage ofOxidizing for 1-4h under the condition of 15-25V, washing with deionized water, and drying with a blast drier to obtain a titanium dioxide nanotube array photoelectrode;
(2) preparing a titanium dioxide nanotube array photoelectrode doped with graphite phase carbon nitride, namely placing carbon nitride powder in ultrapure water for 5-10h by ultrasonic treatment to prepare a carbon nitride solution, coating the carbon nitride solution on the titanium dioxide nanotube array photoelectrode, repeating the process for 3-5 times, placing the titanium dioxide nanotube array photoelectrode in a drying oven at 100 ℃ for drying for 30min, and then placing the titanium dioxide nanotube array photoelectrode in a muffle furnace for annealing at 300-800 ℃ for 1-3h to obtain the titanium dioxide nanotube array photoelectrode doped with graphite phase carbon nitride;
(3) the preparation method of the graphene-doped carbon nitride and graphene titanium dioxide nanotube array photoelectrode comprises the steps of placing graphite oxide in water, ultrasonically stripping for 1-3 hours to obtain graphene oxide dispersion liquid, taking the graphene dispersion liquid as electrolyte, taking the annealed and graphite-doped titanium dioxide nanotube array photoelectrode 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 composite photoelectrode.
2. The method for preparing a composite photoelectrode as claimed in claim 1, wherein the titanium sheet in the step (1) is sequentially polished and polished by 600 mesh, 1000 mesh and 2000 mesh sandpaper before use.
3. The method for preparing a composite photoelectrode as claimed in 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.
4. The method of claim 1, wherein the concentration of NaF in step (1) is 0.2-0.6 wt% and Na is added2SO4The concentration is 0.5-1.5 mol/L.
5. The method for preparing a composite photoelectrode according to claim 1, wherein the coating method in the step (2) comprises the following steps: and (3) dipping the carbon nitride solution by using a brush to coat and load the prepared titanium dioxide nanotube array photoelectrode.
6. The method for preparing a composite photoelectrode according to claim 1, wherein the method for preparing graphite oxide in the step (3) comprises: graphite powder is used as a raw material to prepare water-soluble graphite 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.
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