CN110512260B - Preparation method of composite photoelectrode - Google Patents
Preparation method of composite photoelectrode Download PDFInfo
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- CN110512260B CN110512260B CN201910801174.0A CN201910801174A CN110512260B CN 110512260 B CN110512260 B CN 110512260B CN 201910801174 A CN201910801174 A CN 201910801174A CN 110512260 B CN110512260 B CN 110512260B
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- titanium dioxide
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- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 144
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 94
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 70
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 69
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 52
- 239000010439 graphite Substances 0.000 claims abstract description 45
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 33
- 239000002135 nanosheet Substances 0.000 claims abstract description 25
- 238000001354 calcination Methods 0.000 claims abstract description 19
- 239000002127 nanobelt Substances 0.000 claims abstract description 18
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 50
- 239000002074 nanoribbon Substances 0.000 claims description 40
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 36
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 36
- 239000010936 titanium Substances 0.000 claims description 36
- 229910052719 titanium Inorganic materials 0.000 claims description 36
- 239000008367 deionised water Substances 0.000 claims description 32
- 229910021641 deionized water Inorganic materials 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000003792 electrolyte Substances 0.000 claims description 18
- 229910052697 platinum Inorganic materials 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- 230000003647 oxidation Effects 0.000 claims description 13
- 238000007254 oxidation reaction Methods 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 239000006185 dispersion 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
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 238000000151 deposition Methods 0.000 claims description 11
- 229920000877 Melamine resin Polymers 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 10
- 230000008021 deposition Effects 0.000 claims description 7
- 238000005498 polishing Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000004070 electrodeposition Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 239000012286 potassium permanganate Substances 0.000 claims description 6
- 238000007789 sealing Methods 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
- 238000000967 suction filtration Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000004570 mortar (masonry) Substances 0.000 claims description 5
- 230000035807 sensation Effects 0.000 claims description 5
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 4
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 3
- 238000010298 pulverizing process Methods 0.000 claims 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 8
- 238000000227 grinding Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 7
- 230000001699 photocatalysis Effects 0.000 description 6
- 239000011941 photocatalyst Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- XMEVHPAGJVLHIG-FMZCEJRJSA-N chembl454950 Chemical compound [Cl-].C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H]([NH+](C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O XMEVHPAGJVLHIG-FMZCEJRJSA-N 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000006798 recombination Effects 0.000 description 4
- 238000005215 recombination Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 229960004989 tetracycline hydrochloride Drugs 0.000 description 4
- 238000013329 compounding Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000002071 nanotube Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 1
- 230000032900 absorption of visible light Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- -1 carbon nitrides Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- FIDZUVLGQPMOIN-UHFFFAOYSA-N sodium oxygen(2-) titanium(4+) Chemical compound [O-2].[O-2].[Ti+4].[Na+] FIDZUVLGQPMOIN-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
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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
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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
- B01J35/33—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
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/0605—Binary compounds of nitrogen with carbon
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/19—Preparation by exfoliation
- C01B32/192—Preparation by exfoliation starting from graphitic oxides
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- 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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- 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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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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Abstract
The invention discloses a preparation method of a composite photoelectrode, which belongs to the field of preparation of composite photoelectrodes and comprises the following steps of preparing a titanium dioxide nanobelt array photoelectrode, calcining the photoelectrode to prepare a graphite phase carbon nitride nanosheet colloidal solution, preparing a graphite phase carbon nitride-doped titanium dioxide nanobelt array composite photoelectrode, and preparing a titanium dioxide nanobelt composite photoelectrode with co-deposited graphite phase carbon nitride and graphene.
Description
Technical Field
The invention belongs to the field of composite photoelectrode preparation, and particularly relates to a preparation method of a composite photoelectrode.
Background
Titanium oxide, as a traditional n-type semiconductor photocatalyst, has been widely studied and applied in the field of photocatalysis due to its superior optical and electronic properties, stable physical and chemical properties, no toxic or side effects, low cost and easy availability, and is the most studied photocatalyst material at present. However, titanium dioxide photocatalysts have the following disadvantages: the recombination rate of the photo-generated electrons and the holes is higher; due to TiO2The forbidden band width is wide (3.2 eV), so that the ultraviolet light with energy larger than that of the forbidden band width can be absorbed only, and the utilization rate of the sunlight is low. To improve the above-mentioned defect to TiO2The photocatalyst is modified, the modification method mainly has the functions of noble metal doping, nonmetal doping, semiconductor compounding and surface sensitization, the semiconductor compounding effect is better compared with other modification methods, and the compounding method is diversified.
Carbon nitride has five allotropes, of which graphite phase carbon nitride (g-C)3N4) Is the most stable one of the five carbon nitrides. The nanometer material is environment-friendly, non-toxic, cheap and easily available, belongs to a narrow-bandgap semiconductor, has the bandgap width of about 2.7eV, and has the maximum absorption wavelength of about 460nm, so that the nanometer material can effectively absorb visible light and has higher utilization efficiency on sunlight. At the same time, g-C3N4And has the advantages of good thermal stability, electronic and optical properties and the like. g-C according to the above-mentioned series of excellent characteristics3N4Great attention has been paid to the degradation of organic contaminants under visible light. However, graphite-phase carbon nitride obtained by a thermal polymerization method has the disadvantages of rapid recombination of photo-generated electrons and holes, and the like, and the photocatalytic efficiency is still to be improved. The narrow-band-gap semiconductor graphite-phase carbon nitride is compounded with the wide-band-gap titanium dioxide, so that the visible light absorption range can be improved, the migration of photo-generated electron holes is promoted, and the photocatalyst has high redox capability and finally excellent photocatalytic redox performance. The two-dimensional conductive reduced graphene oxide (rGO) with rich earth content is introduced to serve as an effective electronic medium, so that the transfer of photon-generated carriers is further promoted. Theoretically, rGO not only can increase the contact area and compactness between two different semiconductors by creating a new electron transfer bridge for Z-type charge recombination, but also can greatly improve surface adsorption and reaction kinetics, thereby obviously enhancing the photocatalytic activity.
The current research on the graphene @ graphite phase carbon nitride/titanium dioxide nanoribbon array photoelectrode is less, only the research is mainly focused on the preparation of the graphene @ graphite phase carbon nitride/titanium dioxide nanoribbon array photoelectrode and the graphene @ graphite phase carbon nitride/titanium dioxide powder, and no related report is found yet for the in-situ generation of the Z-type graphene @ graphite phase carbon nitride/titanium dioxide nanoribbon array photoelectrode through thermal polycondensation. The graphene @ graphite phase carbon nitride/titanium dioxide nanotube array photoelectrode has the advantages of being convenient and cheap to recycle, but the graphene @ graphite phase carbon nitride/titanium dioxide array photoelectrode prepared by the method also has the defects in several aspects, the generated graphite phase carbon nitride is deposited on the top of the nanotube in a quantum dot mode, the utilization rate of visible light and the adsorption quantity of pollutants are low, and therefore the photocatalytic efficiency is reduced; the amount of graphite-phase carbon nitride deposited on the titanium dioxide photoelectrode by an anodic oxidation method and a chemical vapor deposition method is very small, and the absorption of visible light and the separation rate of photo-generated electrons and holes are not obviously improved; the separation of the graphene @ graphite phase carbon nitride/titanium dioxide powder from the suspension requires a significant cost which severely hinders the practical application of the process in contaminant treatment.
The technology prepares the bottom titanium dioxide nanotube top nanoribbon array photoelectrode by adjusting anodic oxidation parameters, has the advantages of large specific surface area, high stability, good photoelectrocatalysis performance and the like, and the transmission and transfer capacity of the fixed titanium dioxide photo-generated electrons is further improved by the ordered nanoribbon + tube array. The ordered titanium dioxide array is in semiconductor coupling with graphite-phase carbon nitride and graphene, the valence band top and conduction band bottom energy levels of the titanium dioxide and the graphite-phase carbon nitride are matched, a Z-shaped heterostructure can be formed by the titanium dioxide and the graphite-phase carbon nitride when the titanium dioxide and the graphite-phase carbon nitride are illuminated, photo-generated electrons generated by the titanium dioxide are compounded with holes generated by the graphite-phase carbon nitride, finally the photo-generated holes are gathered on a conduction band of the titanium dioxide, the photo-generated electrons are gathered on the valence band of the graphite-phase carbon nitride, the photo-generated electrons are conducted to the surface of a photoelectrode through the graphene to perform a reduction reaction, the service lives of the photo-generated electrons and the holes are prolonged, meanwhile, photo-generated carriers are effectively separated, and the method.
Disclosure of Invention
The inventor modifies the titanium dioxide nanoribbon array by using graphite-phase carbon nitride and graphene, so that the prepared photocatalyst has higher yield and separation efficiency of photo-generated electron holes, higher visible light utilization performance and obvious effect on photocatalytic degradation of antibiotic tetracycline hydrochloride (TC), and is a preparation method of a green and stable Z-shaped graphene @ graphite-phase carbon nitride/titanium dioxide nanoribbon array photoelectrode.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of a composite photoelectrode comprises the following steps:
s1: preparation of titanium dioxide nanoribbon array photoelectrode
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 0.25-0.75 wt% of NH4F and 100mL of 90-99% glycol, controlling the reaction temperature to be 15-25 ℃, controlling the voltage to be 55-65V, oxidizing for 2-4h, continuously stirring at the rotation speed of 600-800rpm, placing the titanium dioxide nanobelt array photoelectrode after the oxidation in a muffle furnace, and calcining at the temperature of 550 ℃ for 2 h;
s2: preparing a graphite phase carbon nitride nanosheet colloidal solution;
s3: preparing a graphite-phase carbon nitride-doped titanium dioxide nanoribbon array composite photoelectrode;
s4: and preparing the titanium dioxide nanoribbon composite photoelectrode with the codeposited graphite-phase carbon nitride and graphene.
Preferably, the step of titanium sheet pretreatment includes, but is not limited to, cleaning, lapping and polishing, and ultrasonic cleaning.
Preferably, the titanium content in the titanium sheet is more than 99.9%, the specification of the titanium sheet is 100mm multiplied by 10mm multiplied by 0.2mm, 600 meshes, 1000 meshes and 2000 meshes of polished abrasive paper are sequentially selected, ultrasonic cleaning is respectively carried out for 10min in deionized water, acetone and ethanol mixed solution and deionized water, the volume ratio of acetone to ethanol in the acetone and ethanol mixed solution is 1:1, and then the mixture is placed into the deionized water for sealing.
Preferably, in step S2, the melamine is placed in a crucible with a cover, and calcined in a muffle furnace for 2h, with a heating rate of 5 ℃/min, and after the calcination is finished, the melamine is ground by an agate mortar until no obvious granular sensation exists, so as to obtain bulk graphite phase carbon nitride;
putting 3-5g of bulk graphite phase carbon nitride in 50mL of concentrated sulfuric acid, stirring at 25 ℃ to form a turbid liquid, adding the turbid liquid into deionized water, ultrasonically stripping for 10-24h, washing by adopting a suction filtration method to be neutral to obtain graphite phase carbon nitride nanosheets, ultrasonically crushing the carbon nitride nanosheets, and fixing the volume to 2-3L.
Preferably, the melamine is 10-15g, the calcining temperature is 450-550 ℃, the stirring time is 10-24h, the volume of the deionized water is 200-400mL, and the ultrasonic crushing time is 2-3 h.
Preferably, in step S3, 100mL of the graphite-phase carbon nitride nanosheet colloidal solution prepared in step S2 is taken as an electrolyte, a titanium dioxide nanobelt array photoelectrode is taken as a cathode, a platinum sheet is taken as an anode, electrochemical deposition is performed for 30min under a voltage of 1-6V, and drying is performed at a temperature of 101 ℃.
Preferably, in step S4, 10 to 30mg of graphite oxide is taken out of 1L of water, ultrasonic stripping is performed for 1 to 3 hours to obtain a graphene oxide dispersion liquid with a concentration of 10 to 30mg/L, the graphene oxide dispersion liquid is used as an electrolyte, the graphite-phase carbon nitride-doped titanium dioxide nanoribbon array composite photoelectrode prepared in step S3 is used as a cathode, a platinum sheet is used as an anode, the deposition voltage is 1 to 10V, and deposition is performed for 1 to 10 min.
Preferably, 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 for 30min, potassium permanganate solid with the mass being 3-4 times that of the graphite powder is added, the reaction temperature is lower than 10 ℃, the mixture is stirred for 8-10H, water is added, the mixture is stirred for 20-24H at the temperature of 98 ℃, and 30% of H is added2O2And stirring uniformly, washing with 5% HCl and deionized water, and centrifuging and filtering to obtain the graphite oxide.
The invention has the beneficial effects that:
the composite electrode prepared by the invention is economic and environment-friendly, has good stability, mild reaction conditions and easily controlled operation process, overcomes the defects of a titanium dioxide nanobelt array and graphite-phase carbon nitride, widens the spectrum absorption range, reduces the recombination of photoproduction electron holes, is an environment-friendly material with visible light response and high photocatalytic activity, has higher yield and separation efficiency of the photoproduction electron holes and higher visible light utilization performance, and has obvious effect on the photocatalytic degradation of tetracycline hydrochloride (TC).
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example one
A preparation method of a composite photoelectrode comprises the following steps:
firstly, preparing a titanium dioxide nanoribbon array photoelectrode and carrying out calcination treatment.
Cutting a titanium sheet into strip-shaped foil pieces with the thickness of 100mm multiplied by 10mm multiplied by 0.2mm, wherein the titanium content in the titanium sheet is more than 99.9 percent, sequentially cleaning with hydrofluoric acid, and grinding and polishing with 600-mesh, 1000-mesh and 2000-mesh abrasive paper in deionized water and acetone: ultrasonically cleaning the titanium dioxide nanoribbon array in 1:1(vol) ethanol and deionized water for 10min, and sealing the titanium dioxide nanoribbon array in the deionized water to prepare the base material of the titanium dioxide nanoribbon array by anodic oxidation.
Pretreated titanium sheet as anode, platinum sheet of the same size as cathode, electrolyte 0.25 wt% NH4And F and 100mL of 90% glycol, controlling the reaction temperature to be 15 ℃, controlling the voltage to be 55V, oxidizing for 2h, continuously stirring at 600rpm in the anodic oxidation process, generating a titanium dioxide nanoribbon array photoelectrode on the surface of the titanium sheet in situ, and calcining the oxidized titanium sheet in a muffle furnace at 550 ℃ for 2h to obtain the titanium oxide nanoribbon array photoelectrode.
And secondly, preparing a graphite phase carbon nitride nanosheet colloidal solution.
10g of melamine is put into a crucible with a cover and is calcined for 2h at 450 ℃ in a muffle furnace, and the heating rate is 5 ℃/min. After calcining and sintering, grinding the mixture by using an agate mortar until no obvious granular sensation exists, and obtaining the bulk graphite phase carbon nitride. 3g of bulk graphite phase carbon nitride is put into 50mL of concentrated sulfuric acid and stirred for 10 hours at 25 ℃ to obtain a suspension. And adding the turbid liquid into 200mL of deionized water, ultrasonically stripping for 10h, washing to be neutral by using a suction filtration method to obtain graphite-phase carbon nitride nanosheets, ultrasonically crushing the carbon nitride nanosheets for 2h, and fixing the volume to 2L.
And thirdly, preparing the graphite-phase carbon nitride-doped titanium dioxide nanoribbon array composite photoelectrode.
And (3) taking 100mL of the graphite-phase carbon nitride nanosheet colloidal solution prepared in the second step as an electrolyte, taking a titanium dioxide nanobelt array photoelectrode as a cathode and a platinum sheet as an anode, performing electrochemical deposition for 30min under the voltage of 1V, and drying in a drying oven at the temperature of 101 ℃.
And fourthly, preparing the titanium dioxide nano-belt composite photoelectrode with the codeposited graphite phase carbon nitride and graphene.
Preparing graphite oxide by adopting an improved Hummers method, mixing graphite powder and sodium nitrate according to a mass ratio of 1:0.5, adding the mixture into concentrated sulfuric acid, stirring the mixture in an ice bath for 30min, adding potassium permanganate solid with the mass being 3 times that of the graphite powder, stirring the mixture for 8H at the reaction temperature of less than 10 ℃, adding water, stirring the mixture for 20H at the temperature of 98 ℃, adding 30% of H2O2And stirring uniformly, washing with 5% HCl and deionized water, and centrifuging and filtering to obtain the graphite oxide.
And (3) taking 20mg of graphite oxide in 1L of water, ultrasonically stripping for 3h to obtain a graphene oxide dispersion liquid with the concentration of 20mg/L, taking the graphene oxide dispersion liquid as an electrolyte, taking the graphite-phase carbon nitride-doped titanium dioxide nanoribbon array composite photoelectric electrode prepared in the third step as a cathode, taking a platinum sheet as an anode, and depositing for 5min at the deposition voltage of 2V.
Example two
A preparation method of a composite photoelectrode comprises the following steps:
firstly, preparing a titanium dioxide nanoribbon array photoelectrode and carrying out calcination treatment.
Cutting a titanium sheet into strip-shaped foil pieces with the thickness of 100mm multiplied by 10mm multiplied by 0.2mm, wherein the titanium content in the titanium sheet is more than 99.9 percent, cleaning by hydrofluoric acid, sequentially selecting 600-mesh, 1000-mesh and 2000-mesh abrasive paper for grinding and polishing, and respectively adding deionized water and acetone: ultrasonically cleaning ethanol 1:1(vol) and deionized water for 10min, and then placing the cleaned solution into the deionized water for sealing to obtain the base material for preparing the titanium dioxide nanobelt array by anodic oxidation.
The pretreated titanium sheet was used as an anode, a platinum sheet of the same size was used as a cathode, and the electrolyte was 0.5 wt% NH4F and 93 percent glycol 100mL, controlling the reaction temperature at 28 ℃, controlling the voltage at 58V, oxidizing for 2.5h, continuously stirring at 700rpm in the anodic oxidation process, and generating titanium dioxide sodium on the surface of the titanium sheet in situAnd (3) placing the oxidized titanium sheet in a muffle furnace to be calcined for 2 hours at 550 ℃.
And secondly, preparing a graphite phase carbon nitride nanosheet colloidal solution.
12g of melamine was placed in a crucible with a lid and calcined in a muffle furnace at 490 ℃ for 2h with a heating rate of 5 ℃/min. After calcining and sintering, grinding the mixture by using an agate mortar until no obvious granular sensation exists, and obtaining the bulk graphite phase carbon nitride. 3.5g of bulk graphite phase carbon nitride is put into 50mL of concentrated sulfuric acid and stirred for 10 hours at 25 ℃ to obtain a suspension. Adding the turbid liquid into 300mL of deionized water, ultrasonically stripping for 15h, washing by adopting a suction filtration method until the turbid liquid is neutral to obtain graphite-phase carbon nitride nanosheets, ultrasonically crushing the carbon nitride nanosheets for 2.2h, and fixing the volume to 2.2L.
And thirdly, preparing the graphite-phase carbon nitride-doped titanium dioxide nanoribbon array composite photoelectrode.
And (3) taking 100mL of the graphite-phase carbon nitride nanosheet colloidal solution prepared in the second step as an electrolyte, taking a titanium dioxide nanobelt array photoelectrode as a cathode and a platinum sheet as an anode, performing electrochemical deposition for 30min under the voltage of 3V, placing in a drying oven, and drying at the temperature of 101 ℃.
And fourthly, preparing the titanium dioxide nano-belt composite photoelectrode with the codeposited graphite phase carbon nitride and graphene.
Preparing graphite oxide by adopting an improved Hummers method, mixing graphite powder and sodium nitrate according to a mass ratio of 1:0.5, adding the mixture into concentrated sulfuric acid, stirring the mixture in an ice bath for 30min, adding potassium permanganate solid with the mass being 3.2 times that of the graphite powder, stirring the mixture for 9H at the reaction temperature of less than 10 ℃, adding water, stirring the mixture for 22H at the temperature of 98 ℃, adding 30% H2O2And stirring uniformly, washing with 5% HCl and deionized water, and centrifuging and filtering to obtain the graphite oxide.
And (3) taking 15mg of graphite oxide in 1L of water, ultrasonically stripping for 3h to obtain a graphene oxide dispersion liquid with the concentration of 15mg/L, taking the graphene oxide dispersion liquid as an electrolyte, taking the graphite-phase carbon nitride-doped titanium dioxide nanoribbon array composite photoelectric electrode prepared in the third step as a cathode, taking a platinum sheet as an anode, and depositing for 5min at the deposition voltage of 2V.
EXAMPLE III
A preparation method of a composite photoelectrode comprises the following steps:
firstly, preparing a titanium dioxide nanoribbon array photoelectrode and carrying out calcination treatment.
Cutting a titanium sheet into strip-shaped foil pieces with the thickness of 100mm multiplied by 10mm multiplied by 0.2mm, wherein the titanium content in the titanium sheet is more than 99.9 percent, sequentially cleaning the titanium sheet by hydrofluoric acid, and grinding and polishing 600-mesh, 1000-mesh and 2000-mesh abrasive paper in deionized water and acetone respectively: ultrasonically cleaning the titanium dioxide nanoribbon array in 1:1(vol) ethanol and deionized water for 10min, and sealing the titanium dioxide nanoribbon array in the deionized water to prepare the base material of the titanium dioxide nanoribbon array by anodic oxidation.
The pretreated titanium sheet was used as an anode, a platinum sheet of the same size was used as a cathode, and the electrolyte was 0.6 wt% NH4And F and 100mL of 95% glycol mixed solution, controlling the reaction temperature to be 20 ℃, controlling the voltage to be 60V, oxidizing for 3h, continuously stirring at 750rpm in the anodic oxidation process, generating a titanium dioxide nanobelt array photoelectrode on the surface of the titanium sheet in situ, placing the titanium sheet after the oxidation in a muffle furnace, and calcining for 2h at 550 ℃.
And secondly, preparing a graphite phase carbon nitride nanosheet colloidal solution.
Putting 13g of melamine into a crucible with a cover, putting the crucible into a muffle furnace at 520 ℃, calcining for 2h at the heating rate of 5 ℃/min, and grinding the crucible by using an agate mortar until no obvious granular sensation exists after the calcination is finished to obtain the bulk graphite phase carbon nitride.
4g of bulk graphite phase carbon nitride is put into 50mL of concentrated sulfuric acid and stirred for 10 hours at 25 ℃ to obtain suspension. And adding the turbid liquid into 350mL of deionized water, ultrasonically stripping for 20h, washing by adopting a suction filtration method until the turbid liquid is neutral to obtain graphite-phase carbon nitride nanosheets, ultrasonically crushing the carbon nitride nanosheets for 2.5h, and fixing the volume to 2.5L.
And thirdly, preparing the graphite-phase carbon nitride-doped titanium dioxide nanoribbon array composite photoelectrode.
And (3) taking 100mL of the graphite-phase carbon nitride nanosheet colloidal solution prepared in the second step as an electrolyte, taking a titanium dioxide nanobelt array photoelectrode as a cathode and a platinum sheet as an anode, performing electrochemical deposition for 30min under the voltage of 5V, and drying in a drying oven at the temperature of 101 ℃.
And fourthly, preparing the titanium dioxide nano-belt composite photoelectrode with the codeposited graphite phase carbon nitride and graphene.
Preparing graphite oxide by adopting an improved Hummers method, mixing graphite powder and sodium nitrate according to a mass ratio of 1:0.5, adding the mixture into concentrated sulfuric acid, stirring the mixture in an ice bath for 30min, adding potassium permanganate solid with the mass being 3.5 times that of the graphite powder, stirring the mixture for 9.5H at a reaction temperature of less than 10 ℃, adding water, stirring the mixture for 23H at a temperature of 98 ℃, adding 30% of H2O2And stirring uniformly, washing with 5% HCl and deionized water, and centrifuging and filtering to obtain the graphite oxide.
And (3) taking 20mg of graphite oxide in 1L of water, ultrasonically stripping for 3h to obtain a graphene oxide dispersion liquid with the concentration of 20mg/L, taking the graphene oxide dispersion liquid as an electrolyte, taking the graphite-phase carbon nitride-doped titanium dioxide nanoribbon array composite photoelectrode prepared in the third step as a cathode, taking a platinum sheet as an anode, and depositing for 5min at the deposition voltage of 2V.
Example four
A preparation method of a composite photoelectrode comprises the following steps:
firstly, preparing a titanium dioxide nanoribbon array photoelectrode and carrying out calcination treatment.
Cutting a titanium sheet into strip-shaped foil pieces with the thickness of 100mm multiplied by 10mm multiplied by 0.2mm, wherein the titanium content in the titanium sheet is more than 99.9 percent, sequentially cleaning the titanium sheet by hydrofluoric acid, and grinding and polishing 600-mesh, 1000-mesh and 2000-mesh abrasive paper in deionized water and acetone respectively: ultrasonically cleaning the titanium dioxide nanoribbon array in 1:1(vol) ethanol and deionized water for 10min, and sealing the titanium dioxide nanoribbon array in the deionized water to prepare the base material of the titanium dioxide nanoribbon array by anodic oxidation.
The pretreated titanium sheet was used as an anode, a platinum sheet of the same size was used as a cathode, and the electrolyte was 0.75 wt% NH4And F and 100mL of 99% glycol, controlling the reaction temperature to be 25 ℃, controlling the voltage to be 65V, oxidizing for 4h, continuously stirring at 800rpm in the anodic oxidation process, generating a titanium dioxide nanoribbon array photoelectrode in situ on the surface of the titanium sheet, placing the oxidized titanium sheet in a muffle furnace at 550 ℃, and calcining for 2 h.
And secondly, preparing a graphite phase carbon nitride nanosheet colloidal solution.
15g of melamine is placed in a crucible with a cover and calcined in a muffle furnace at 550 ℃ for 2h, with the heating rate of 5 ℃/min. After calcining and sintering, grinding the mixture by agate until no obvious granular feeling exists, and obtaining the bulk graphite phase carbon nitride.
5g of bulk graphite phase carbon nitride is put into 50mL of concentrated sulfuric acid and stirred for 10 hours at 25 ℃ to obtain a suspension. Adding the suspension into 400mL of deionized water, ultrasonically stripping for 24h, washing to be neutral by adopting a suction filtration method to obtain graphite-phase carbon nitride nanosheets, ultrasonically crushing the carbon nitride nanosheets for 3h, and fixing the volume to 3L.
And thirdly, preparing the graphite-phase carbon nitride-doped titanium dioxide nanoribbon array composite photoelectrode.
And (3) taking 100mL of the graphite-phase carbon nitride nanosheet colloidal solution prepared in the second step as an electrolyte, taking a titanium dioxide nanobelt array photoelectrode as a cathode and a platinum sheet as an anode, performing electrochemical deposition for 30min under the voltage of 5V, and drying in a drying oven at the temperature of 101 ℃.
And fourthly, preparing the titanium dioxide nano-belt composite photoelectrode with the codeposited graphite phase carbon nitride and graphene.
Preparing graphite oxide by adopting an improved Hummers method, mixing graphite powder and sodium nitrate according to a mass ratio of 1:0.5, adding the mixture into concentrated sulfuric acid, stirring the mixture in an ice bath for 30min, adding potassium permanganate solid with the mass being 4 times that of the graphite powder, stirring the mixture for 10H at the reaction temperature of less than 10 ℃, adding water, stirring the mixture for 24H at the temperature of 98 ℃, adding 30% H2O2And stirring uniformly, washing with 5% HCl and deionized water, and centrifuging and filtering to obtain the graphite oxide.
And (3) taking 30mg of graphene oxide in 1L of water, ultrasonically stripping for 3h to obtain a graphene oxide dispersion liquid with the concentration of 30mg/L, taking the graphene oxide dispersion liquid as an electrolyte, taking the graphite-phase carbon nitride-doped titanium dioxide nanoribbon array composite photoelectrode prepared in the third step as a cathode, taking a platinum sheet as an anode, and depositing for 5min to obtain the graphene oxide/carbon nitride/titanium dioxide nanoribbon composite photoelectrode.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (8)
1. The preparation method of the composite photoelectrode is characterized by comprising the following steps of:
s1: preparation of titanium dioxide nanoribbon array photoelectrode
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 0.25-0.75 wt% of NH4F and 100mL of 90-99% glycol, controlling the reaction temperature to be 15-25 ℃, controlling the voltage to be 55-65V, oxidizing for 2-4h, continuously stirring at the rotation speed of 600-800rpm, placing the titanium dioxide nanobelt array photoelectrode after the oxidation in a muffle furnace, and calcining at the temperature of 550 ℃ for 2 h;
s2: preparing a graphite phase carbon nitride nanosheet colloidal solution;
s3: preparing a graphite-phase carbon nitride-doped titanium dioxide nanoribbon array composite photoelectrode;
s4: and preparing the titanium dioxide nanoribbon composite photoelectrode with the codeposited graphite-phase carbon nitride and graphene.
2. The method of claim 1, wherein the step of pre-treating the titanium sheet includes but is not limited to cleaning, polishing and ultrasonic cleaning.
3. The method for preparing the composite photoelectrode as claimed in claim 2, wherein the titanium content in the titanium sheet is more than 99.9%, the specification of the titanium sheet is 100mm x 10mm x 0.2mm, 600 meshes, 1000 meshes and 2000 meshes of abrasive paper for polishing are sequentially selected, ultrasonic cleaning is respectively carried out for 10min in deionized water, acetone and ethanol mixed solution and deionized water, the volume ratio of acetone to ethanol in the acetone and ethanol mixed solution is 1:1, and then the mixture is placed in deionized water for sealing.
4. The method for preparing the composite photoelectrode as claimed in claim 2, wherein in step S2, the melamine is placed in a crucible with a cover, the crucible is calcined in a muffle furnace for 2 hours at a heating rate of 5 ℃/min, and after the calcination is finished, the melamine is ground by an agate mortar until no obvious granular sensation exists, so that bulk graphite phase carbon nitride can be prepared;
putting 3-5g of bulk graphite phase carbon nitride in 50mL of concentrated sulfuric acid, stirring at 25 ℃ to form a turbid liquid, adding the turbid liquid into deionized water, ultrasonically stripping for 10-24h, washing by adopting a suction filtration method to be neutral to obtain graphite phase carbon nitride nanosheets, ultrasonically crushing the carbon nitride nanosheets, and fixing the volume to 2-3L.
5. The method for preparing a composite photoelectrode as claimed in claim 4, wherein the melamine is 10-15g, the calcination temperature is 450-550 ℃, the stirring time is 10-24h, the volume of the deionized water is 200-400mL, and the ultrasonic pulverization time is 2-3 h.
6. The method for preparing the composite photoelectrode as claimed in claim 2, wherein in step S3, 100mL of the graphite phase carbon nitride nanosheet colloidal solution prepared in step S2 is taken as an electrolyte, the titanium dioxide nanobelt array photoelectrode is taken as a cathode, the platinum sheet is taken as an anode, electrochemical deposition is carried out for 30min under the voltage of 1-6V, and drying is carried out at the temperature of 101 ℃.
7. The method for preparing the composite photoelectrode as claimed in claim 2, wherein in step S4, 10-30 mg of graphite oxide is taken into 1L of water, ultrasonic stripping is carried out for 1-3 h to obtain a graphene oxide dispersion liquid with the concentration of 10-30 mg/L, the graphene oxide dispersion liquid is used as an electrolyte, the graphite-phase carbon nitride doped titanium dioxide nanoribbon array composite photoelectrode prepared in step S3 is used as a cathode, a platinum sheet is used as an anode, the deposition voltage is 1-10V, and deposition is carried out for 1-10 min.
8. The preparation method of the composite photoelectrode, as claimed in claim 7, is characterized in that graphite powder and sodium nitrate are mixed according to a mass ratio of 1:0.5, added into concentrated sulfuric acid, stirred in an ice bath for 30min, potassium permanganate solid with a mass 3-4 times that of the graphite powder is added, the reaction temperature is lower than 10 ℃, stirred for 8-10H, added with water, stirred for 20-24H at a temperature of 98 ℃, added with 30% of H2O2And stirring uniformly, washing with 5% HCl and deionized water, and centrifuging and filtering to obtain the graphite oxide.
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