CN106745534A - A kind of composite photocatalyst electrode of photo-reduction metal-modified cobaltosic oxide/titanium dioxide p n hetero-junctions and its preparation - Google Patents
A kind of composite photocatalyst electrode of photo-reduction metal-modified cobaltosic oxide/titanium dioxide p n hetero-junctions and its preparation Download PDFInfo
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- CN106745534A CN106745534A CN201611258308.1A CN201611258308A CN106745534A CN 106745534 A CN106745534 A CN 106745534A CN 201611258308 A CN201611258308 A CN 201611258308A CN 106745534 A CN106745534 A CN 106745534A
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- electrode
- titanium dioxide
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- composite photocatalyst
- cobaltosic oxide
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 103
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000002131 composite material Substances 0.000 title claims abstract description 14
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 11
- 238000007540 photo-reduction reaction Methods 0.000 title claims abstract description 7
- 239000002071 nanotube Substances 0.000 claims abstract description 34
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 24
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052709 silver Inorganic materials 0.000 claims abstract description 17
- 239000004332 silver Substances 0.000 claims abstract description 16
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052737 gold Inorganic materials 0.000 claims abstract description 10
- 239000010931 gold Substances 0.000 claims abstract description 10
- 239000010936 titanium Substances 0.000 claims abstract description 10
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 10
- QXPOCKAMMVZJDU-UHFFFAOYSA-L [Co++].CC([O-])=O.CC([O-])=O.OCCO Chemical compound [Co++].CC([O-])=O.CC([O-])=O.OCCO QXPOCKAMMVZJDU-UHFFFAOYSA-L 0.000 claims abstract description 9
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002105 nanoparticle Substances 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 6
- 238000012545 processing Methods 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 6
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims abstract description 5
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims abstract description 5
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 9
- 239000011651 chromium Substances 0.000 abstract description 6
- 238000006722 reduction reaction Methods 0.000 abstract description 5
- 230000009467 reduction Effects 0.000 abstract description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052804 chromium Inorganic materials 0.000 abstract description 3
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 17
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 15
- 239000003054 catalyst Substances 0.000 description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 238000007743 anodising Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 239000008151 electrolyte solution Substances 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 4
- 239000007832 Na2SO4 Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 229960000907 methylthioninium chloride Drugs 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 230000005622 photoelectricity Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- -1 01M gold chlorides Chemical class 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 241001062009 Indigofera Species 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- SJUCACGNNJFHLB-UHFFFAOYSA-N O=C1N[ClH](=O)NC2=C1NC(=O)N2 Chemical compound O=C1N[ClH](=O)NC2=C1NC(=O)N2 SJUCACGNNJFHLB-UHFFFAOYSA-N 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- IUJHOHSBALVOLS-UHFFFAOYSA-N [Co]=O.[O-2].[Ti+4].[O-2] Chemical compound [Co]=O.[O-2].[Ti+4].[O-2] IUJHOHSBALVOLS-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- SVMCDCBHSKARBQ-UHFFFAOYSA-N acetic acid;cobalt Chemical compound [Co].CC(O)=O SVMCDCBHSKARBQ-UHFFFAOYSA-N 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical class [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical class [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 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
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006181 electrochemical material Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001595 flow curve Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
- C02F2001/46138—Electrodes comprising a substrate and a coating
- C02F2001/46142—Catalytic coating
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/4612—Controlling or monitoring
- C02F2201/46125—Electrical variables
- C02F2201/46135—Voltage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/4612—Controlling or monitoring
- C02F2201/4615—Time
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/4618—Supplying or removing reactants or electrolyte
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
Composite photocatalyst electrode the invention discloses a kind of photo-reduction metal-modified cobaltosic oxide/titanium dioxide p n hetero-junctions and preparation method thereof, (1) titania nanotube is soaked in silver nitrate or gold chloride or platinum acid chloride solution, 0.5~1.5h is stirred under normal temperature, inert gas drying after separation of solid and liquid, 0.5~2h of ultraviolet light, obtains to surface the titanium dioxide nanotube electrode for covering and carrying silver or gold or Pt nanoparticle；(2) titanium dioxide nanotube electrode that step (1) is prepared is immersed in cobalt acetate ethylene glycol solution, then carries out separation of solid and liquid and vacuum dried successively and calcination processing obtains composite photocatalyst electrode.With the composite photocatalyst electrode, titanium sheet as negative electrode, it is biased 1~3V, 1~3h of electrolysis treatment.Combination electrode p-nitrophenyl removal of the invention and chromium reduction have preferable effect.
Description
Technical field
Prepared the invention belongs to catalysis material nano material and environmental pollution purification applications technical field, and in particular to
A kind of preparation method of metal-modified cobaltosic oxide nano particle/titania nanotube p-n heterojunction photochemical catalyst.
Background technology
In recent years, photocatalysis technology is considered as always energy problem and the most potential means of environmental pollution of solving, and
TiO2It has been still photochemical catalyst of greatest concern since being found from 1972.In order to solve TiO2What can not be maximally utilized can
See the shortcoming of light, researchers are from TiO2Synthesis and modified angle set out, such as sol-gel process, template, hydro-thermal method,
Seeded growth method and anodizing prepare titanium dioxide, by methods such as element doping, noble metal loading, semiconductors couplings
To the titania modified utilization to promote to visible ray.
Cobaltosic oxide (Co3O4), the theoretical capacity high and the excellent cycle performance that are showed in lithium ion battery by it and
It is widely studied, there is scholar's research Co3O4Influence of the calcining heat to its chemical property.Result shows that calcining heat is shadow
The key factor of its performance is rung, because temperature directly influences Co3O4Granular size and pattern.In numerous researchs, Co3O4's
Chemical property is received significant attention, but its photocatalytic performance rarely has research.
The content of the invention
The present invention provides a kind of photochemical catalyst synthetic method of simple easily system, and practical application effect stability and high efficiency, can
Synergistic degradation organic matter and heavy metal Cr VI mixed pollutants
A kind of preparation of the composite photocatalyst electrode of photo-reduction metal-modified cobaltosic oxide/titanium dioxide p-n heterojunction
Method, comprises the following steps：
(1) titania nanotube is soaked in silver nitrate or gold chloride or platinum acid chloride solution, under normal temperature stir 0.5~
1.5h, inert gas drying, 0.5~2h of ultraviolet light after separation of solid and liquid, obtain to surface and cover load silver or gold or Pt nanoparticle
Titanium dioxide nanotube electrode；
(2) titanium dioxide nanotube electrode that step (1) is prepared is immersed in cobalt acetate ethylene glycol solution, then
Carry out separation of solid and liquid and vacuum dried successively and calcination processing obtains composite photocatalyst electrode.
Co3O4As p-type semiconductor, by with N-type TiO2Formed P-N junction to form built in field favorable electron hole
Separate, relative to single titanium dioxide, methyl orange is solved in the case where visible ray is dropped by the cobalt oxide titanium dioxide electrodes modified and is contaminated
It is more preferable that material is showed, and cobaltosic oxide not only shows excellent in electrochemical material, while also there is good photocatalysis performance.
Although P-N junction type electrode effectively suppresses the light induced electron transmission between conduction band between electron-hole recombinations, semiconductor
Also certain obstacle, the present invention introduces noble metal on two kinds of contact surfaces of material can promote light induced electron to shift, and work as
When noble metal (such as gold, silver) is with N-type semiconductor combination, the surface plasma resonance effect (SPR) of generation can allow both combinations
Body has very strong sink effect to visible ray.
The present invention uses photo-reduction technology, is irradiated one hour under the conditions of ultraviolet, you can noble silver is supported on into dioxy
Change on titanium nanotube so that metallics is covered in cobaltosic oxide/titanium dioxide electrodes surface in the form of nanometer layer,
Even, film is thin, stabilization；Ternary heterojunction structure is formed between cobaltosic oxide, silver or gold or platinum and titanium dioxide.Silver is present in
Between titanium dioxide and cobaltosic oxide.When noble metal (such as gold, silver) is with N-type semiconductor combination, the surface plasma of generation
Resonance effects (SPR) can allow both combinations to have very strong sink effect to visible ray.And Co3O4As p-type semiconductor,
By with N-type TiO2Favorable electron hole separates to form built in field to form PN junction.Enhance the suction for visible ray
Receive, promote hole to produce, be conducive to producing the lasting separation in hole again.
Described photo catalytic reduction of the invention refers to containing Ag+、Au+、Pt+The aqueous solution mix with titanium dioxide, in uviol lamp
The lower Titanium dioxide absorption band-gap energy of irradiation, produces electron hole pair, and Ag is made under light induced electron effect+、Au+、Pt+In TiO2Table
Face carries out reduction reaction, and metal Ag, Au, the Pt being reduced are deposited directly to TiO2On surface, good complex is formed.Light is also
Former method have be evenly distributed, film forming is thin, low cost and other advantages, has preferable performance for depositing nano level film layer.
The titania nanotube is prepared by anodizing, can also be obtained by approach purchased in market, anodizing
Comprise the following steps that：
By titanium sheet successively with the sand papering of 400,800,1200 mesh, after it is clear with acetone, ethanol, deionized water ultrasound successively
15min is washed, is dried stand-by.With titanium sheet as anode, nickel sheet is negative electrode, and oxalic acid and ammonium fluoride are electrolyte solution, electricity under the conditions of 20V
Solution 2h, flushing afterwards is dried stand-by.
Inert gas used is N2, ultra violet lamp is using 500W xenon lamps.
Preferably, the concentration of the silver nitrate solution is 0.01~0.4M.More preferably 0.2~0.3M；Most preferably
It is 0.23M.
The concentration of the chlorauric acid solution is 0.001~0.1M6.More preferably 0.01M；The platinum acid chloride solution
Concentration is 0.001~0.1M.More preferably 0.01M.Gold chloride and chloroplatinic acid belong to valuables, using the few control of amount
Method, deposition will be less than silver.
It is advisable with by whole titania nanotube submergences when titania nanotube is soaked in silver nitrate solution.
Preferably, the concentration of the cobalt acetate ethylene glycol solution is 0.01~0.1M.More preferably 0.01-0.03M,
Most preferably 0.03M.With by titania nanotube when titanium dioxide nanotube electrode is immersed in cobalt acetate ethylene glycol solution
All submergence is advisable electrode.
Ad hoc structure, phase between each composition are formed in the present invention between noble metal, titanium dioxide and cobaltosic oxide three
Mutually collaboration improves the photocatalysis performance of electrode jointly, and what is prepared in the range of above-mentioned optimum ratio between three kinds of compositions is compound
Photochemical catalyst electrode performance is more excellent.
Preferably, soak time is 30~90min during titanium dioxide nanotube electrode is immersed in cobalt acetate ethylene glycol solution,
More preferably 30~40min；Most preferably 30min.
Described vacuum drying is vacuum dried 30min to be placed in vacuum tube drying box, and the temperature of vacuum drying chamber is
80℃。
Preferably, the calcination processing is that dry electrode is placed in tube furnace, N2Held at 350~500 DEG C under atmosphere
Continuous 1~3h.
The present invention also provides the composite photocatalyst electrode that a kind of preparation method as described is prepared.Prepared by the present invention
Electrode is visible light-responded electrode.
The present invention also provides a kind of electrochemical process for treating of organic polluting water, comprises the following steps：With described compound
Photochemical catalyst electrode, titanium sheet are negative electrode, are biased 1~3V, 1~3h of electrolysis treatment.
Combination electrode p-nitrophenyl removal of the invention and chromium reduction have preferable effect.
Electrolyte solution is 0.1M Na2SO4, it is preferable that the organic pollution is methylene blue.
Preferably, 2V is biased in electrolytic process, electrolytic processing time is 2h.
The beneficial effects of the invention are as follows：Using stable titania nanotube as carrier, by simple photoreduction met hod
With thermal decomposition method synthetic catalyst, preparation process concrete conditions in the establishment of a specific crime composite catalyst excellent catalytic effect easy to control, prepared, and circulation
Repeatedly it still is able to keep excellent catalytic activity, has a extensive future.
Brief description of the drawings
Fig. 1 is the photoelectric current of the cobaltosic oxide silver titania nanotube photoelectrocatalysielectrode electrode that embodiment 1 is prepared
Figure
Fig. 2 is the electrode photoelectric flow graph of various concentrations cobaltosic oxide.
Fig. 3 is the electrode photoelectric flow graph of various concentrations silver nitrate.
Fig. 4 is the cobaltosic oxide silver titania nanotube photoelectrocatalysielectrode electrode ESEM that embodiment 1 is prepared
Figure.
Fig. 5 is the EDS map of the cobaltosic oxide silver titania nanotube photoelectrocatalysielectrode electrode that embodiment 1 is prepared
Figure.
Fig. 6 is the electrode photoelectric flow graph for carrying gold or platinum.
Fig. 7 is the cobaltosic oxide silver titania nanotube photoelectrocatalysielectrode electrode degraded methylene that embodiment 1 is prepared
The visible absorption spectrum of base is with light application time variation diagram.
Fig. 8 is the cobaltosic oxide silver titania nanotube photoelectrocatalysielectrode electrode degraded methylene that embodiment 1 is prepared
Base indigo plant stable circulation type test result figure.
Fig. 9 is nitrobenzene degradation and chromium reduction curve map.
Specific embodiment
Embodiment 1
(1) preparation of nano-silver loaded titanium dioxide nanotube electrode
Anodizing prepares titania nanotube：Prepare the mixing of 100ml 0.135M ammonium fluorides and 0.116M oxalic acid
Solution, to dissolving, with titanium sheet as anode, nickel sheet builds battery for negative electrode, and 2 are reacted under 20V voltages for stirring on magnetic stirring apparatus
Hour, you can must be by the titania nanotube prepared by anodizing.
Titania nanotube is immersed in the silver nitrate solution 1h (under the conditions of stirring at normal temperature) of 40g/L, after use N2Drying,
0.5h under 500W xenon lamp ultraviolet lights is placed in, is obtained to surface and is covered the titanium dioxide nanotube electrode of silver-carrying nano particle.Pass through again
Same method prepares silver nitrate concentration for the titanium dioxide that silver-carrying nano particle is covered on the surface of 1.7g/L, 17g/L, 68g/L is received
Mitron electrode.
(2) preparation of cobaltosic oxide silver titania nanotube：The electrode prepared in step (1) is immersed in
In 0.15M cobalt acetate ethylene glycol solutions, persistently soak 30min, after be placed in vacuum tube drying box and be vacuum dried 30min, so
Dry electrode is placed in tube furnace afterwards, N2Continue 2h under atmosphere at 350~500 DEG C, obtain composite photoelectric catalyst prod.
LSV signs are carried out to electrode using CHI660E electrochemical workstations, be can be seen that from LSV photoelectricity flow graph (such as Fig. 1)
Cobaltosic oxide has very big lifting to the photoelectric properties of titania nanotube, and after silver nano-grain is mixed, property
Can be even more and be greatly improved.
Change 4 kinds of acetic acid cobalt concentrations, from 0.1M~1M, electrode photoelectric flow curve is obtained, shown in Fig. 2.It can be found that when dense
When degree is more than 0.03M, the photocurrent response change of electrode is little, therefore optimal 0.03M cobalt acetates are used in subsequent experimental
Concentration is prepared.
Change 4 kinds of silver nitrate concentrations, respectively 1.7g/L, 17g/L, 40g/L, 68g/L (0.01M, 0.1M, 0.23M,
0.4M), corresponding photocurrent curve figure is obtained, as shown in figure 3, effect when caning be found that silver nitrate concentration is 40g/L from figure
It is substantially better than other concentration.
Surface topography table is carried out to combination electrode prepared by embodiment 1 using field emission scanning electron microscope (such as Fig. 4)
Levying, and be aided with EDS map proves its Elemental redistribution.The success of silver-colored cobaltosic oxide nano particle is can be seen that in figure and is equably divided
On titania nanotube, Fig. 5 demonstrates the presence of Co/Ag elements and each element is evenly distributed to cloth for EDS figures.
Embodiment 2
Silver nitrate solution is substituted using 0.01M gold chlorides or platinum acid chloride solution on the basis of embodiment 1, due to gold chloride
Or chloroplatinic acid is more valuable, therefore deposited using low concentration, equally soak 1h (under the conditions of stirring at normal temperature), after use N2Drying,
0.5h under 500W xenon lamp ultraviolet lights is placed in, is obtained to surface and is covered the titania nanotube electricity for carrying gold or Pt nanoparticle
Pole.The step of using embodiment 1 again supported cobaltosic oxide, obtains composite photoelectric catalyst prod.
LSV signs are carried out to electrode using CHI660E electrochemical workstations, be can be seen that from LSV photoelectricity flow graph (such as Fig. 6)
Cobaltosic oxide has very big lifting to the photoelectric properties of titania nanotube, and is mixing gold or Pt nanoparticle
Afterwards, performance can also be greatly improved.
Embodiment 3
The combination electrode prepared using embodiment (1) processes 20mg/L methylene blue solutions, and condition is：Be biased for
2V, electrolyte solution is 0.1M Na2SO4, combination electrode is anode, and titanium sheet is negative electrode, and the reaction time is 2h.Experimental result is as schemed
Shown in 7, it is seen that after 2h, the clearance of methylene blue is more than 90%.
The combination electrode prepared using embodiment (1) processes 20mg/L methylene blue solutions, and condition is：Be biased for
2V, electrolyte solution is 0.1M Na2SO4, combination electrode is anode, and titanium sheet is negative electrode, and the reaction time is 2h.It is repeated 4 times experiment.
Experimental result is as shown in Figure 8, it is seen that repeatedly catalytic effect is not affected after circulation.
Embodiment 4
The combination electrode prepared using embodiment (1) processes 20mg/L nitrobenzene and Cr VI mixed solution, and condition is：Apply
2V is biased at, electrolyte solution is 0.1M Na2SO4, combination electrode is anode, and titanium sheet is negative electrode, and the reaction time is 50min.
Experimental result is as shown in Figure 9, it is seen that after 50min, the clearance of nitrobenzene more than 90%, the reduction of Cr VI 75% with
On.
The specific implementation case of patent of the present invention is the foregoing is only, but the technical characteristic of patent of the present invention is not limited to
This, any those skilled in the relevant art in the field of the invention, all cover of the invention special by the change or modification made
Among sharp scope.
Claims (7)
1. a kind of preparation side of the composite photocatalyst electrode of photo-reduction metal-modified cobaltosic oxide/titanium dioxide p-n heterojunction
Method, it is characterised in that comprise the following steps：
(1) titania nanotube is soaked in silver nitrate or gold chloride or platinum acid chloride solution, under normal temperature stir 0.5~
1.5h, inert gas drying, 0.5~2h of ultraviolet light after separation of solid and liquid, obtain to surface and cover load silver or gold or Pt nanoparticle
Titanium dioxide nanotube electrode；
(2) titanium dioxide nanotube electrode that step (1) is prepared is immersed in cobalt acetate ethylene glycol solution, is then carried out
Separation of solid and liquid and successively vacuum dried and calcination processing obtain composite photocatalyst electrode.
2. preparation method according to claim 1, it is characterised in that the concentration of the silver nitrate solution is 0.01~0.4M.
3. preparation method according to claim 1, it is characterised in that the concentration of the cobalt acetate ethylene glycol solution is 0.01~
0.1M。
4. preparation method according to claim 1, it is characterised in that titanium dioxide nanotube electrode is molten in cobalt acetate ethylene glycol
Soak time is 30~90min in liquid.
5. preparation method according to claim 1, it is characterised in that the calcination processing is that dry electrode is placed in into tubular type
In stove, N2Continue 1~3h at 350~500 DEG C under atmosphere.
6. the composite photocatalyst electrode that a kind of preparation method as described in Claims 1 to 5 any claim is prepared.
7. a kind of electrochemical process for treating of organic polluting water, it is characterised in that comprise the following steps：With claim 6 institute
Composite photocatalyst electrode is stated for anode, titanium sheet are negative electrode, are biased 1~3V, 1~3h of electrolysis treatment.
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|---|---|---|---|---|
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| CN108525667A (en) * | 2018-04-10 | 2018-09-14 | 苏州大学 | Metal organic frame derives the preparation method of the TiO 2 nanotubes modified array of cobaltosic oxide |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150133293A1 (en) * | 2013-11-09 | 2015-05-14 | Sensiran | Method for deposition of noble metal nanoparticles on catalysts to promote same, and the compositions so produced |
| CN104923225A (en) * | 2014-03-18 | 2015-09-23 | 中国科学院大连化学物理研究所 | Supported noble metal catalyst and preparation and application thereof |
| CN105664969A (en) * | 2016-01-23 | 2016-06-15 | 武汉理工大学 | Titanium dioxide-platinum-tricobalt tetraoxide tri-element composite photocatalytic material and preparation method thereof |
-
2016
- 2016-12-30 CN CN201611258308.1A patent/CN106745534B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150133293A1 (en) * | 2013-11-09 | 2015-05-14 | Sensiran | Method for deposition of noble metal nanoparticles on catalysts to promote same, and the compositions so produced |
| CN104923225A (en) * | 2014-03-18 | 2015-09-23 | 中国科学院大连化学物理研究所 | Supported noble metal catalyst and preparation and application thereof |
| CN105664969A (en) * | 2016-01-23 | 2016-06-15 | 武汉理工大学 | Titanium dioxide-platinum-tricobalt tetraoxide tri-element composite photocatalytic material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| J. H.芬德勒等: "《纳米粒子与纳米结构薄膜》", 29 August 2003, 化学工业出版社 * |
| YU-WENCHEN等: "Au/Co3O4–TiO2 catalysts for preferential oxidation of CO in H2 stream", 《JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107199038A (en) * | 2017-07-07 | 2017-09-26 | 湖北大学 | A kind of composite photo-catalyst and preparation method thereof |
| CN107199038B (en) * | 2017-07-07 | 2020-03-31 | 湖北大学 | Composite photocatalyst and preparation method thereof |
| CN108525667A (en) * | 2018-04-10 | 2018-09-14 | 苏州大学 | Metal organic frame derives the preparation method of the TiO 2 nanotubes modified array of cobaltosic oxide |
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