CN109553162A - It is a kind of using ordered porous ZnO as the stainless steel base nano array β-PbO of template2The preparation method of electrode - Google Patents
It is a kind of using ordered porous ZnO as the stainless steel base nano array β-PbO of template2The preparation method of electrode Download PDFInfo
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- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 162
- 239000010935 stainless steel Substances 0.000 title claims abstract description 162
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000004793 Polystyrene Substances 0.000 claims abstract description 135
- 229920002223 polystyrene Polymers 0.000 claims abstract description 133
- 239000004005 microsphere Substances 0.000 claims abstract description 112
- 239000002356 single layer Substances 0.000 claims abstract description 84
- 239000007788 liquid Substances 0.000 claims abstract description 82
- 229910006654 β-PbO2 Inorganic materials 0.000 claims abstract description 79
- 238000004070 electrodeposition Methods 0.000 claims abstract description 29
- 238000007743 anodising Methods 0.000 claims abstract description 18
- 238000010276 construction Methods 0.000 claims abstract description 15
- 239000003960 organic solvent Substances 0.000 claims abstract description 15
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 229910000831 Steel Inorganic materials 0.000 claims description 88
- 239000010959 steel Substances 0.000 claims description 88
- 239000000243 solution Substances 0.000 claims description 78
- 238000000034 method Methods 0.000 claims description 34
- 239000002243 precursor Substances 0.000 claims description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000000758 substrate Substances 0.000 claims description 22
- 230000004913 activation Effects 0.000 claims description 16
- 230000003647 oxidation Effects 0.000 claims description 15
- 238000007254 oxidation reaction Methods 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 239000002094 self assembled monolayer Substances 0.000 claims description 14
- 239000013545 self-assembled monolayer Substances 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 239000001509 sodium citrate Substances 0.000 claims description 13
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Inorganic materials [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 12
- 230000015556 catabolic process Effects 0.000 claims description 11
- 238000006731 degradation reaction Methods 0.000 claims description 11
- 239000011592 zinc chloride Substances 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 238000004090 dissolution Methods 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000011534 incubation Methods 0.000 claims description 7
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 5
- 125000003944 tolyl group Chemical group 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- 239000010815 organic waste Substances 0.000 claims description 3
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 244000248349 Citrus limon Species 0.000 claims 1
- 235000005979 Citrus limon Nutrition 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 238000002242 deionisation method Methods 0.000 claims 1
- 238000000227 grinding Methods 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 239000007772 electrode material Substances 0.000 abstract description 23
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 230000007797 corrosion Effects 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 4
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002086 nanomaterial Substances 0.000 abstract 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 7
- 238000005498 polishing Methods 0.000 description 6
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 6
- 239000011805 ball Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000593 degrading effect Effects 0.000 description 5
- 239000011806 microball Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000010842 industrial wastewater Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead(II) nitrate Inorganic materials [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 241000555268 Dendroides Species 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- -1 has physical method Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000003466 welding 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
-
- 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
- C02F2101/30—Organic compounds
-
- 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
- C02F2101/32—Hydrocarbons, e.g. oil
-
- 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
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of using ordered porous ZnO as the stainless steel base nano array β-PbO of template2The preparation method of electrode, belongs to PbO2Electrode material technical field.The present invention prepares single layer polystyrene microsphere template using liquid surface construction from part in stainless steel base；Orderly ZnO nano material is prepared using hydrothermal reaction at low temperature；PS microballoon is removed using organic solvent, and uses H3BO3Solution carries out through-hole to the hole left after removal PS microballoon and obtains ordered porous ZnO nano template；Using anodizing, in the hole of ordered porous ZnO nano template, electrodeposited nanocrystalline β-PbO2Particle utilizes H3BO3Solution removes ZnO nano template, again electro-deposition nanometer β-PbO2The stainless steel base nano array β-PbO that particle preparation specific surface area dramatically increases2Electrode.Electrode of the present invention has bigger specific surface area, electro catalytic activity and better corrosion resistance.
Description
Technical field
The present invention relates to a kind of using ordered porous ZnO as the stainless steel base nano array β-PbO of template2The preparation side of electrode
Method belongs to metal oxide PbO2Electrode technology field.
Background technique
With the continuous development of national economy, using welding as cost the problem of is further highlighted, and is generated therefrom
Problem of environmental pollution is also more serious.As industrial wastewater without processing with regard to including in these waste water the problems such as uncontrolled discharge
There are many hardly degraded organic substance, such as various pesticides, dyestuff, aromatic compound etc., these substances can not be decomposed by nature to be inhaled
It receives, remains in various waters and soil always.The method for being conventionally used to degradation of organic substances waste water mainly has physical method, chemical method
And bioanalysis, but there is complex process, low efficiency, at high cost and be easy to cause secondary pollution etc. and ask always for these methods
Topic.
For poisonous and hazardous aromatic hydrocarbon substance in industrial wastewater of degrading and significantly improves its degradation efficiency and reduces energy consumption,
Electrochemical treatments technology catalytic activity, it is convenient, efficient, in terms of have a clear superiority, principle is using additional
Power supply degradation of organic substances directly in electrochemical reactor, or strong oxidizing property is generated by redox reactions some on electrode
Free radical degrades indirectly to organic matter, therefore research and development have the novel inert anode material of higher catalytic activity and stability
It is imperative.
There are metal electrode, nonmetallic compound electrode in the electrode for being used for aromatic hydrocarbon substance in degradation of organic waste water at this stage
And metal oxide electrode etc., wherein studied in metal oxide electrode it is more be PbO2Electrode, wherein Pb is in
Its highest price oxidation state has strong oxidizing property, and oxygen evolution potential is high, catalytic performance is good, but still remains problems, such as table
Face active layer is easy to fall off, and stability is still lower with catalytic activity, and the PbO after use2Electrode will appear hole and knot
Structure defect.
Summary of the invention
For metal oxide PbO in the prior art2Electrode active surface layer is easy to fall off, and stability and catalytic activity are still
Lower problem, the present invention provide a kind of using ordered porous ZnO as the stainless steel base nano array β-PbO of template2The system of electrode
Preparation Method, due to forming orderly rough PbO in matrix surface2Nano-array significantly increases its specific surface area, living
Property number of loci increased significantly, and catalytic activity significantly improves.Electrode of the present invention overpotential for oxygen evolution with higher, electro catalytic activity
With higher corrosion resistance.
It is a kind of using ordered porous ZnO as the stainless steel base nano array β-PbO of template2The preparation method of electrode is specific to walk
It is rapid as follows:
(1) using stainless steel plate as substrate, using liquid surface construction from part in stainless steel plate substrate self-assembled monolayer polystyrene
Microsphere template obtains stainless base steel/single layer polystyrene microsphere template；
(2) stainless steel plate of step (1)/single layer polystyrene microsphere template is placed in precursor solution, using low-temperature hydrothermal
Legal system has sequence nano-ZnO template and obtains stainless base steel/single layer polystyrene microsphere/ordered nano ZnO template；Wherein presoma
Solution is ZnCl2Sodium citrate aqueous solution, the pH value of precursor solution are 10 ~ 11；
(3) using in organic solvent dissolution removal step (2) stainless base steel/single layer polystyrene microsphere/ordered nano ZnO template
Single layer polystyrene microsphere, and use H3BO3Solution carries out through-hole to the hole left after removal single layer polystyrene microsphere and obtains
To stainless base steel/porous nano ZnO template；Wherein organic solvent is toluene, methylene chloride, tetrahydrofuran or acetone；
(4) using stainless base steel/porous nano ZnO template of step (3) as anode, stainless steel plate is cathode, in electroplate liquid, is adopted
With anodizing in stainless base steel/porous nano ZnO template hole electro-deposition nanometer β-PbO2Obtain stainless base steel/more
Hole nano-ZnO/nano-array β-PbO2；
(5) by stainless base steel/porous nano ZnO/nanometer β-PbO2It is placed in H3BO3It is impregnated in solution and removes ordered porous ZnO template
Obtain stainless steel base/nano array β-PbO2；
(6) with the stainless steel base/nano array β-PbO of step (5)2For anode, stainless steel plate is cathode, in electroplate liquid, then
It is secondary to use anodizing in stainless steel base/nano array β-PbO2Lattice structure on electro-deposition nanometer β-PbO2Up to stainless
Base steel nano-array β-PbO2Electrode.
Step (1) stainless steel plate is to carry out pretreated activation stainless steel plate, wherein pretreatment includes stainless steel plate
Surface spikes, oxidation film are removed through polishing, oil removing is washed and is dried；5 ~ 10 min of activation in hydrochloric acid solution are subsequently placed in,
It washes, be dried to obtain activation stainless steel plate；
The step (1) uses liquid surface construction from part self-assembled monolayer polystyrene microsphere template in stainless steel plate substrate
Specific method be monodisperse polystyrene microsphere stoste is added to dehydrated alcohol and carry out 1 ~ 5min of ultrasound obtain polystyrene/
Dehydrated alcohol mixed liquor instills polystyrene/dehydrated alcohol mixed liquor in deionized water under the conditions of temperature is 20 ~ 30 DEG C
It stands and generates single layer polystyrene microsphere film, stainless steel base is inserted into deionized water with being greater than 45° angle, it is poly- to single layer
Taking-up is dried to obtain stainless base steel/single layer polystyrene microsphere template after phenylethylene micro ball is uniformly paved with stainless steel base；Wherein
The concentration of monodisperse polystyrene microsphere stoste is 25 ~ 50 g/L, and the partial size of monodisperse polystyrene microsphere is 5 ~ 10 μm；Single point
The volume ratio for dissipating polystyrene microsphere stoste and dehydrated alcohol is 4:(3 ~ 2)；
ZnCl in precursor solution in precursor solution in the step (2)2Concentration is 0.1 ~ 0.3 mol/L, sodium citrate
Concentration is 0.2 ~ 0.8 g/L；
Using hydrothermal reaction at low temperature preparing orderly nano-ZnO template in the step (2), to obtain stainless base steel/single layer polystyrene micro-
The specific steps are stainless steel plate/single layer polystyrene microsphere template is placed in precursor solution for ball/ordered nano ZnO template
In, incubation water heating reacts 1 ~ 5h under the conditions of temperature is 80 ~ 100 DEG C, takes out cooling, washes and be drying to obtain stainless base steel/mono-
Strata phenylethylene micro ball/ordered nano ZnO template；
The H3BO3The concentration of solution is 0.05 ~ 0.50 mol/L；
The electroplate liquid is Pb (NO3)2-NaF-Cu(NO3)2Electroplate liquid, the pH value of electroplate liquid are 2 ~ 3；
Pb (NO in the electroplate liquid3)2Concentration is 190.0 ~ 210.0 g/L, and NaF concentration is 0.5 ~ 0.8 g/L, Cu (NO3)2 It is dense
Degree is 15.0 ~ 30.0 g/L；
The temperature of step (4) the Anodic Oxidation method is 30 ~ 60 DEG C, and DC current density is 10 ~ 15mA/cm2, direct current is heavy
The long-pending time is 20 ~ 30min；
The temperature of step (6) the Anodic Oxidation method is 30 ~ 60 DEG C, and DC current density is 10 ~ 15mA/cm2, direct current is heavy
The long-pending time is 10 ~ 30min；
Stainless steel base nano array β-PbO of the invention2Electrode can be used as aromatic hydrocarbon substance electrode in degradation industrial organic waste water
Application.
Beneficial effects of the present invention:
(1) its coating surface of nano-array electrode material of the present invention shows the raised lattice structure of rule, and specific surface area is significant
Increase, the electro catalytic activity of electrode material is remarkably improved, to solve common plane β-PbO2Electrode specific surface area is small, electro-catalysis
The problems such as activity is low；
(2) nano-array electrode material of the present invention is using stainless steel plate as substrate, cheap and easy acquisition, and stainless
Steel base and β-PbO2The advantages that binding force of cladding material is superior, and internal stress is small；
(3) nano-array electrode material of the present invention is using ordered porous ZnO film material as template, compared to other templates
Speech, ZnO template preparation process is simple and low in raw material price, and is suitable for large-scale use；
(4) its ordered porous ZnO template of nano-array electrode material of the present invention uses H3BO3Solution carries out through-hole and dissolution, energy
Enough utilize H3BO3The faintly acid of solution effectively controls its through-hole and course of dissolution, forms it into ordered porous ZnO
Template, in order to subsequent β-PbO2The formation of lattice structure；
(5) its layer electrodes crystal grain of nano-array electrode material of the present invention is tiny, and corrosion resistance is more preferable, can preferably prevent base
Body is damaged, and increases the service life of electrode material；
(6) nano-array electrode material of the present invention is for when the degradation of aromatic hydrocarbon substance, electrode material electricity to be urged in organic wastewater
The advantages that changing superior performance, being provided simultaneously with higher degradation efficiency, excellent corrosion resistance and low energy consumption.
Detailed description of the invention
Fig. 1 is process flow chart of the invention；
Fig. 2 is stainless steel base nano array β-PbO made from embodiment 12The SEM of electrode schemes；
Fig. 3 is stainless steel base nano array β-PbO made from embodiment 22The SEM of electrode schemes；
Fig. 4 is stainless steel base nano array β-PbO made from embodiment 32The SEM of electrode schemes；
Fig. 5 is stainless steel base nano array β-PbO made from embodiment 42The SEM of electrode schemes；
Fig. 6 is stainless steel base nano array β-PbO made from embodiment 52The SEM of electrode schemes；
Fig. 7 is stainless steel base plane β-PbO2Electrode and stainless steel base nano array β-PbO2The removal rate of electrode degrading phenol with
The variation diagram of time；
Fig. 8 is the stainless steel base nano array β-PbO prepared under the conditions of different embodiments2The removal rate of electrode degrading phenol is at any time
Between variation diagram.
Specific embodiment
Invention is further described in detail With reference to embodiment, but protection scope of the present invention and unlimited
In the content.
The stainless steel base nano array β-PbO of the embodiment of the present invention2The electrocatalysis characteristic of electrode is studied: stainless with embodiment
Base steel nano-array β-PbO2Electrode is anode, and stainless steel plate of the same area is cathode, DC power supply power supply, using two electrodes
System simulates industrial wastewater by target contaminant of phenol, and Pyrogentisinic Acid carries out Electrocatalysis Degradation, as experimental group；Using common
β-the PbO of plane2The stainless steel base nano array β-PbO of electrode and embodiment2For electrode respectively as anode, remaining condition is constant,
Pyrogentisinic Acid carries out Electrocatalysis Degradation；The volume of phenol solution is 1000mL, concentration 100mg/L, current density 30mA/cm2。
Embodiment 1: as shown in Figure 1, a kind of using ordered porous ZnO as the stainless steel base nano array β-PbO of template2Electrode
Preparation method, the specific steps are as follows:
(1) using stainless steel plate as substrate, using liquid surface construction from part in stainless steel plate substrate self-assembled monolayer polystyrene
Microsphere template obtains stainless base steel/single layer polystyrene microsphere template；Wherein stainless steel plate is that the pretreated activation of progress is stainless
Steel plate, wherein pretreatment includes stainless steel plate through polishing removing surface spikes, oxidation film, oil removing is washed and is dried；Then
It is placed in hydrochloric acid solution and activates 5 min, wash, be dried to obtain activation stainless steel plate；
Use the specific method of liquid surface construction from part self-assembled monolayer polystyrene microsphere template in stainless steel plate substrate for
Monodisperse polystyrene microsphere stoste is added to dehydrated alcohol and carries out ultrasonic 3min and obtains polystyrene/dehydrated alcohol mixing
Polystyrene/dehydrated alcohol mixed liquor is instilled standing generation single layer in deionized water and gathered by liquid under the conditions of temperature is 25 DEG C
Stainless steel base is inserted into deionized water by phenylethylene micro ball film with being greater than 45° angle, uniform to single layer polystyrene microsphere
Taking-up is dried to obtain stainless base steel/single layer polystyrene microsphere template after being paved with stainless steel base；Wherein monodisperse polystyrene
The concentration of microballoon stoste is 25g/L, and the partial size of monodisperse polystyrene microsphere is 8 μm；Monodisperse polystyrene microsphere stoste with
The volume ratio of dehydrated alcohol is 4:3；
(2) stainless steel plate of step (1)/single layer polystyrene microsphere template is placed in precursor solution, using low-temperature hydrothermal
Legal system has sequence nano-ZnO template and obtains stainless base steel/single layer polystyrene microsphere/ordered nano ZnO template；Wherein presoma
Solution is ZnCl2Sodium citrate aqueous solution, the pH value of precursor solution are 10.5；In precursor solution in precursor solution
ZnCl2Concentration is 0.20 mol/L, and the concentration of sodium citrate is 0.5 g/L；
Orderly nano-ZnO template is prepared using hydrothermal reaction at low temperature and obtains stainless base steel/single layer polystyrene microsphere/ordered nano
ZnO template the specific steps are stainless steel plate/single layer polystyrene microsphere template is placed in precursor solution, be 95 in temperature
Incubation water heating reacts 2.0h under the conditions of DEG C, takes out cooling, washing and being drying to obtain stainless base steel/single layer polystyrene microsphere/has
Sequence nano-ZnO template；
(3) use organic solvent (organic solvent is toluene) dissolution removal step (2) stainless base steel/single layer polystyrene microsphere/
Single layer polystyrene microsphere in ordered nano ZnO template, and use H3BO3Solution to removal single layer polystyrene microsphere after stay
Under hole carry out through-hole obtain stainless base steel/porous nano ZnO template；Wherein H3BO3The concentration of solution is 0.30 mol/L；
(4) using stainless base steel/porous nano ZnO template of step (3) as anode, stainless steel plate is cathode, in electroplate liquid, is adopted
With anodizing in stainless base steel/porous nano ZnO template hole electro-deposition nanometer β-PbO2Obtain stainless base steel/more
Hole nano-ZnO/nano-array β-PbO2；Wherein electroplate liquid is Pb (NO3)2-NaF-Cu(NO3)2The pH value of electroplate liquid, electroplate liquid is
2.5；Pb (NO in electroplate liquid3)2Concentration is 190.0 g/L, and NaF concentration is 0.5 g/L, Cu (NO3)2 Concentration is 15.0 g/
L；The temperature of anodizing is 40 DEG C, and DC current density is 12.5 mA/cm2, the time of DC electrodeposition is 20min；
(5) by stainless base steel/porous nano ZnO/nanometer β-PbO2It is placed in H3BO3It is impregnated in solution and removes ordered porous ZnO template
Obtain stainless steel base/nano array β-PbO2；Wherein H3BO3The concentration of solution is 0.35mol/L；
(6) with the stainless steel base/nano array β-PbO of step (5)2For anode, stainless steel plate is cathode, in electroplate liquid, is adopted
With anodizing in stainless steel base/nano array β-PbO2Hole in electro-deposition nanometer β-PbO2Up to stainless base steel nanometer
Array β-PbO2Electrode；Wherein electroplate liquid is Pb (NO3)2-NaF-Cu(NO3)2Electroplate liquid, the pH value of electroplate liquid are 2.5；Electroplate liquid
Middle Pb (NO3)2Concentration is 190.0 g/L, and NaF concentration is 0.5 g/L, Cu (NO3)2 Concentration is 15.0 g/L, anodic oxidation
The temperature of method is 40 DEG C, DC current density 12.5mA/cm2, the DC electrodeposition time is 20min.
Stainless steel base nano array β-PbO through this embodiment2The SEM figure (see figure 2) of electrode, stainless steel base nano array
β-PbO2Electrode material has the significant raised lattice structure of rule, with common plane β-PbO2Electrode material compares, raised points
Battle array structure increases the number of active sites of electro-catalysis, the specific surface area of electrocatalytic reaction is effectively increased, to improve
Electrocatalysis characteristic.
Embodiment 2: as shown in Figure 1, a kind of using ordered porous ZnO as the stainless steel base nano array β-PbO of template2Electrode
Preparation method, the specific steps are as follows:
(1) using stainless steel plate as substrate, using liquid surface construction from part in stainless steel plate substrate self-assembled monolayer polystyrene
Microsphere template obtains stainless base steel/single layer polystyrene microsphere template；Wherein stainless steel plate is that the pretreated activation of progress is stainless
Steel plate, wherein pretreatment includes stainless steel plate through polishing removing surface spikes, oxidation film, oil removing is washed and is dried；Then
It is placed in hydrochloric acid solution and activates 5 min, wash, be dried to obtain activation stainless steel plate；
Use the specific method of liquid surface construction from part self-assembled monolayer polystyrene microsphere template in stainless steel plate substrate for
Monodisperse polystyrene microsphere stoste is added to dehydrated alcohol and carries out ultrasonic 3min and obtains polystyrene/dehydrated alcohol mixing
Polystyrene/dehydrated alcohol mixed liquor is instilled in deionized water under the conditions of temperature is 25 DEG C and stands generation single layer polyphenyl by liquid
Stainless steel base is inserted into deionized water with being greater than 45° angle, is uniformly spread to single layer polystyrene microsphere by ethylene microballoon film
It is taken out after full stainless steel base and is dried to obtain stainless base steel/single layer polystyrene microsphere template；Wherein monodisperse polystyrene is micro-
The concentration of ball stoste is 25g/L, and the partial size of monodisperse polystyrene microsphere is 8 μm；Monodisperse polystyrene microsphere stoste and nothing
The volume ratio of water-ethanol is 4:3；
(2) stainless steel plate of step (1)/single layer polystyrene microsphere template is placed in precursor solution, using low-temperature hydrothermal
Legal system has sequence nano-ZnO template and obtains stainless base steel/single layer polystyrene microsphere/ordered nano ZnO template；Wherein presoma
Solution is ZnCl2Sodium citrate aqueous solution, the pH value of precursor solution are 10.5；In precursor solution in precursor solution
ZnCl2Concentration is 0.2 mol/L, and the concentration of sodium citrate is 0.20g/L；
Orderly nano-ZnO template is prepared using hydrothermal reaction at low temperature and obtains stainless base steel/single layer polystyrene microsphere/ordered nano
ZnO template the specific steps are stainless steel plate/single layer polystyrene microsphere template is placed in precursor solution, be 90 in temperature
Under the conditions of DEG C incubation water heating react 2h, take out cooling, wash and be drying to obtain stainless base steel/single layer polystyrene microsphere/orderly
Nano-ZnO template；
(3) use organic solvent (organic solvent is toluene) dissolution removal step (2) stainless base steel/single layer polystyrene microsphere/
Single layer polystyrene microsphere in ordered nano ZnO template, and use H3BO3Solution to removal single layer polystyrene microsphere after stay
Under hole carry out through-hole obtain stainless base steel/porous nano ZnO template；Wherein H3BO3The concentration of solution is 0.10mol/L；
(4) using stainless base steel/porous nano ZnO template of step (3) as anode, stainless steel plate is cathode, in electroplate liquid, is adopted
With anodizing in stainless base steel/porous nano ZnO template hole electro-deposition nanometer β-PbO2Obtain stainless base steel/more
Hole nano-ZnO/nano-array β-PbO2；Wherein electroplate liquid is Pb (NO3)2-NaF-Cu(NO3)2The pH value of electroplate liquid, electroplate liquid is
2；Pb (NO in electroplate liquid3)2Concentration is 190.0g/L, and NaF concentration is 0.5g/L, Cu (NO3)2 Concentration is 15.0g/L；Anodic oxygen
The temperature of change method is 40 DEG C, DC current density 10mA/cm2, the time of DC electrodeposition is 30min；
(5) by stainless base steel/porous nano ZnO/nanometer β-PbO2It is placed in H3BO3It is impregnated in solution and removes ordered porous ZnO template
Obtain stainless steel base/nano array β-PbO2；Wherein H3BO3The concentration of solution is 0.25mol/L；
(6) with the stainless steel base/nano array β-PbO of step (5)2For anode, stainless steel plate is cathode, in electroplate liquid, then
It is secondary to use anodizing in stainless steel base/nano array β-PbO2Lattice structure on electro-deposition nanometer β-PbO2Up to stainless
Base steel nano-array β-PbO2Electrode；Wherein electroplate liquid is Pb (NO3)2-NaF-Cu(NO3)2Electroplate liquid, the pH value of electroplate liquid are 2；
Pb (NO in electroplate liquid3)2Concentration is 190.0g/L, and NaF concentration is 0.5g/L, Cu (NO3)2 Concentration is 15.0g/L, anodic oxidation
The temperature of method is 40 DEG C, DC current density 10mA/cm2, the DC electrodeposition time is 20min.
Pass through stainless steel base nano array β-PbO2The SEM figure (see figure 3) of electrode is it is found that made from through this embodiment not
Become rusty base steel nano-array β-PbO2Electrode material has the raised nutty structure of more rules, but surface compared to embodiment 1
Particle reduces and the lattice structure of rule is reduced；But its catalytically active surface product and common plane β-PbO2Electrode material compares
Still increase, also effectively increase the specific surface area of electrocatalytic reaction, to improve electrocatalysis characteristic.
Embodiment 3: as shown in Figure 1, a kind of using ordered porous ZnO as the stainless steel base nano array β-PbO of template2Electrode
Preparation method, the specific steps are as follows:
(1) using stainless steel plate as substrate, using liquid surface construction from part in stainless steel plate substrate self-assembled monolayer polystyrene
Microsphere template obtains stainless base steel/single layer polystyrene microsphere template；Wherein stainless steel plate is that the pretreated activation of progress is stainless
Steel plate, wherein pretreatment includes stainless steel plate through polishing removing surface spikes, oxidation film, oil removing is washed and is dried；Then
It is placed in hydrochloric acid solution and activates 8 min, wash, be dried to obtain activation stainless steel plate；
Use the specific method of liquid surface construction from part self-assembled monolayer polystyrene microsphere template in stainless steel plate substrate for
Monodisperse polystyrene microsphere stoste is added to dehydrated alcohol and carries out ultrasonic 1min and obtains polystyrene/dehydrated alcohol mixing
Polystyrene/dehydrated alcohol mixed liquor is instilled in deionized water under the conditions of temperature is 20 DEG C and stands generation single layer polyphenyl by liquid
Stainless steel base is inserted into deionized water with being greater than 45° angle, is uniformly spread to single layer polystyrene microsphere by ethylene microballoon film
It is taken out after full stainless steel base and is dried to obtain stainless base steel/single layer polystyrene microsphere template；Wherein monodisperse polystyrene is micro-
The concentration of ball stoste is 30 g/L, and the partial size of monodisperse polystyrene microsphere is 5 μm；Monodisperse polystyrene microsphere stoste and nothing
The volume ratio of water-ethanol is 4:2.5；
(2) stainless steel plate of step (1)/single layer polystyrene microsphere template is placed in precursor solution, using low-temperature hydrothermal
Legal system has sequence nano-ZnO template and obtains stainless base steel/single layer polystyrene microsphere/ordered nano ZnO template；Wherein presoma
Solution is ZnCl2Sodium citrate aqueous solution, the pH value of precursor solution are 10.0；In precursor solution in precursor solution
ZnCl2Concentration is 0.15 mol/L, and the concentration of sodium citrate is 0.20 g/L；
Orderly nano-ZnO template is prepared using hydrothermal reaction at low temperature and obtains stainless base steel/single layer polystyrene microsphere/ordered nano
ZnO template the specific steps are stainless steel plate/single layer polystyrene microsphere template is placed in precursor solution, be 85 in temperature
Incubation water heating reacts 4.5h under the conditions of DEG C, takes out cooling, washing and being drying to obtain stainless base steel/single layer polystyrene microsphere/has
Sequence nano-ZnO template；
(3) use organic solvent (organic solvent is methylene chloride) dissolution removal step (2) stainless base steel/single layer polystyrene micro-
Single layer polystyrene microsphere in ball/ordered nano ZnO template, and use H3BO3After solution is to removal single layer polystyrene microsphere
The hole left carries out through-hole and obtains stainless base steel/porous nano ZnO template；Wherein H3BO3The concentration of solution is 0.35 mol/
L；
(4) using stainless base steel/porous nano ZnO template of step (3) as anode, stainless steel plate is cathode, in electroplate liquid, is adopted
With anodizing in stainless base steel/porous nano ZnO template hole electro-deposition nanometer β-PbO2Obtain stainless base steel/more
Hole nano-ZnO/nano-array β-PbO2；Wherein electroplate liquid is Pb (NO3)2-NaF-Cu(NO3)2The pH value of electroplate liquid, electroplate liquid is
2.5；Pb (NO in electroplate liquid3)2Concentration is 200.0 g/L, and NaF concentration is 0.6 g/L, Cu (NO3)2 Concentration is 20.0 g/L；Sun
The temperature of pole oxidizing process is 50 DEG C, DC current density 10mA/cm2, the time of DC electrodeposition is 20min；
(5) by stainless base steel/porous nano ZnO/nanometer β-PbO2It is placed in H3BO3It is impregnated in solution and removes ordered porous ZnO template
Obtain stainless steel base/nano array β-PbO2；Wherein H3BO3The concentration of solution is 0.10mol/L；
(6) with the stainless steel base/nano array β-PbO of step (5)2For anode, stainless steel plate is cathode, in electroplate liquid, is adopted
With anodizing in stainless steel base/nano array β-PbO2Hole in electro-deposition nanometer β-PbO2Up to stainless base steel nanometer
Array β-PbO2Electrode；Wherein electroplate liquid is Pb (NO3)2-NaF-Cu(NO3)2Electroplate liquid, the pH value of electroplate liquid are 2.5；Electroplate liquid
Middle Pb (NO3)2Concentration is 200.0 g/L, and NaF concentration is 0.6 g/L, Cu (NO3)2 Concentration is 20.0 g/L, anodic oxidation
The temperature of method is 50 DEG C, DC current density 10mA/cm2, the DC electrodeposition time is 10min.
Pass through stainless steel base nano array β-PbO2The SEM figure (Fig. 4) of electrode is it is found that obtained stainless through this embodiment
Base steel nano-array β-PbO2Electrode material has similar raised lattice structure compared to embodiment 1, but surface particles shape is also
Not molding completely；But its catalytically active surface product and common plane β-PbO2Electrode material, which compares, still to be increased, also effectively
The specific surface area of electrocatalytic reaction is increased, to improve electrocatalysis characteristic.
Embodiment 4: as shown in Figure 1, a kind of using ordered porous ZnO as the stainless steel base nano array β-PbO of template2Electrode
Preparation method, the specific steps are as follows:
(1) using stainless steel plate as substrate, using liquid surface construction from part in stainless steel plate substrate self-assembled monolayer polystyrene
Microsphere template obtains stainless base steel/single layer polystyrene microsphere template；Wherein stainless steel plate is that the pretreated activation of progress is stainless
Steel plate, wherein pretreatment includes stainless steel plate through polishing removing surface spikes, oxidation film, oil removing is washed and is dried；Then
It is placed in hydrochloric acid solution and activates 10 min, wash, be dried to obtain activation stainless steel plate；
Use the specific method of liquid surface construction from part self-assembled monolayer polystyrene microsphere template in stainless steel plate substrate for
Monodisperse polystyrene microsphere stoste is added to dehydrated alcohol and carries out ultrasonic 5min and obtains polystyrene/dehydrated alcohol mixing
Polystyrene/dehydrated alcohol mixed liquor is instilled standing generation single layer in deionized water and gathered by liquid under the conditions of temperature is 30 DEG C
Stainless steel base is inserted into deionized water by phenylethylene micro ball film with being greater than 45° angle, uniform to single layer polystyrene microsphere
Taking-up is dried to obtain stainless base steel/single layer polystyrene microsphere template after being paved with stainless steel base；Wherein monodisperse polystyrene
The concentration of microballoon stoste is 35g/L, and the partial size of monodisperse polystyrene microsphere is 10 μm；Monodisperse polystyrene microsphere stoste with
The volume ratio of dehydrated alcohol is 4:2；
(2) stainless steel plate of step (1)/single layer polystyrene microsphere template is placed in precursor solution, using low-temperature hydrothermal
Legal system has sequence nano-ZnO template and obtains stainless base steel/single layer polystyrene microsphere/ordered nano ZnO template；Wherein presoma
Solution is ZnCl2Sodium citrate aqueous solution, the pH value of precursor solution are 11；ZnCl in precursor solution in precursor solution2
Concentration is 0.3mol/L, and the concentration of sodium citrate is 0.8g/L；
Orderly nano-ZnO template is prepared using hydrothermal reaction at low temperature and obtains stainless base steel/single layer polystyrene microsphere/ordered nano
ZnO template the specific steps are stainless steel plate/single layer polystyrene microsphere template is placed in precursor solution, be in temperature
Incubation water heating reacts 1h under the conditions of 100 DEG C, takes out cooling, washing and being drying to obtain stainless base steel/single layer polystyrene microsphere/has
Sequence nano-ZnO template；
(3) use organic solvent (organic solvent is tetrahydrofuran) dissolution removal step (2) stainless base steel/single layer polystyrene micro-
Single layer polystyrene microsphere in ball/ordered nano ZnO template, and use H3BO3After solution is to removal single layer polystyrene microsphere
The hole left carries out through-hole and obtains stainless base steel/porous nano ZnO template；Wherein H3BO3The concentration of solution is 0.45 mol/
L；
(4) using stainless base steel/porous nano ZnO template of step (3) as anode, stainless steel plate is cathode, in electroplate liquid, is adopted
With anodizing in stainless base steel/porous nano ZnO template hole electro-deposition nanometer β-PbO2Obtain stainless base steel/more
Hole nano-ZnO/nano-array β-PbO2；Wherein electroplate liquid is Pb (NO3)2-NaF-Cu(NO3)2The pH value of electroplate liquid, electroplate liquid is
3；Pb (NO in electroplate liquid3)2Concentration is 190.0 g/L, NaF concentration 0.5 g/L, Cu (NO3)2 Concentration is 15.0 g/L；Anode
The temperature of oxidizing process is 60 DEG C, DC current density 15mA/cm2, the time of DC electrodeposition is 20min；
(5) by stainless base steel/porous nano ZnO/nanometer β-PbO2It is placed in H3BO3It is impregnated in solution and removes ordered porous ZnO template
Obtain stainless steel base/nano array β-PbO2；Wherein H3BO3The concentration of solution is 0.45 mol/L；
(6) with the stainless steel base/nano array β-PbO of step (5)2For anode, stainless steel plate is cathode, in electroplate liquid, is adopted
With anodizing in stainless steel base/nano array β-PbO2Hole in electro-deposition nanometer β-PbO2Up to stainless base steel nanometer
Array β-PbO2Electrode；Wherein electroplate liquid is Pb (NO3)2-NaF-Cu(NO3)2Electroplate liquid, the pH value of electroplate liquid are 3；In electroplate liquid
Pb(NO3)2Concentration is 190.0 g/L, and NaF concentration is 0.5 g/L, Cu (NO3)2 Concentration is 15.0 g/L, anodizing
Temperature is 60 DEG C, DC current density 15mA/cm2, the DC electrodeposition time is 30min.
Pass through stainless steel base nano array β-PbO2The SEM figure (see figure 5) of electrode is it is found that made from through this embodiment not
Become rusty base steel nano-array β-PbO2Electrode material has the similar raised nutty structure of rule, but its table compared to embodiment 1
Face graininess partial size significantly increases.But its catalytically active surface product and common plane β-PbO2Electrode material, which compares, still to be increased
Add, also effectively increase the specific surface area of electrocatalytic reaction, to also improve electrocatalysis characteristic.
Embodiment 5: as shown in Figure 1, a kind of using ordered porous ZnO as the stainless steel base nano array β-PbO of template2Electrode
Preparation method, the specific steps are as follows:
(1) using stainless steel plate as substrate, using liquid surface construction from part in stainless steel plate substrate self-assembled monolayer polystyrene
Microsphere template obtains stainless base steel/single layer polystyrene microsphere template；Wherein stainless steel plate is that the pretreated activation of progress is stainless
Steel plate, wherein pretreatment includes stainless steel plate through polishing removing surface spikes, oxidation film, oil removing is washed and is dried；Then
It is placed in hydrochloric acid solution and activates 5 min, wash, be dried to obtain activation stainless steel plate；
Use the specific method of liquid surface construction from part self-assembled monolayer polystyrene microsphere template in stainless steel plate substrate for
Monodisperse polystyrene microsphere stoste is added to dehydrated alcohol and carries out ultrasonic 3min and obtains polystyrene/dehydrated alcohol mixing
Polystyrene/dehydrated alcohol mixed liquor is instilled standing generation single layer in deionized water and gathered by liquid under the conditions of temperature is 25 DEG C
Stainless steel base is inserted into deionized water by phenylethylene micro ball film with being greater than 45° angle, uniform to single layer polystyrene microsphere
Taking-up is dried to obtain stainless base steel/single layer polystyrene microsphere template after being paved with stainless steel base；Wherein monodisperse polystyrene
The concentration of microballoon stoste is 50 g/L, and the partial size of monodisperse polystyrene microsphere is 8 μm；Monodisperse polystyrene microsphere stoste with
The volume ratio of dehydrated alcohol is 4:3；
(2) stainless steel plate of step (1)/single layer polystyrene microsphere template is placed in precursor solution, using low-temperature hydrothermal
Legal system has sequence nano-ZnO template and obtains stainless base steel/single layer polystyrene microsphere/ordered nano ZnO template；Wherein presoma
Solution is ZnCl2Sodium citrate aqueous solution, the pH value of precursor solution are 10.5；In precursor solution in precursor solution
ZnCl2Concentration is 0.20mol/L, and the concentration of sodium citrate is 0.5g/L；
Orderly nano-ZnO template is prepared using hydrothermal reaction at low temperature and obtains stainless base steel/single layer polystyrene microsphere/ordered nano
ZnO template the specific steps are stainless steel plate/single layer polystyrene microsphere template is placed in precursor solution, be 90 in temperature
Incubation water heating reacts 2.0h under the conditions of DEG C, takes out cooling, washing and being drying to obtain stainless base steel/single layer polystyrene microsphere/has
Sequence nano-ZnO template；
(3) use organic solvent (organic solvent is acetone) dissolution removal step (2) stainless base steel/single layer polystyrene microsphere/
Single layer polystyrene microsphere in ordered nano ZnO template, and use H3BO3Solution to removal single layer polystyrene microsphere after stay
Under hole carry out through-hole obtain stainless base steel/porous nano ZnO template；Wherein H3BO3The concentration of solution is 0.08mol/L；
(4) using stainless base steel/porous nano ZnO template of step (3) as anode, stainless steel plate is cathode, in electroplate liquid, is adopted
With anodizing in stainless base steel/porous nano ZnO template hole electro-deposition nanometer β-PbO2Obtain stainless base steel/more
Hole nano-ZnO/nano-array β-PbO2；Wherein electroplate liquid is Pb (NO3)2-NaF-Cu(NO3)2The pH value of electroplate liquid, electroplate liquid is
2；Pb (NO in electroplate liquid3)2Concentration is 210.0 g/L, and NaF concentration is 0.8 g/L, Cu (NO3)2 Concentration is 30.0 g/L；Sun
The temperature of pole oxidizing process is 50 DEG C, and DC current density is 10 mA/cm2, the time of DC electrodeposition is 30min；
(5) by stainless base steel/porous nano ZnO/nanometer β-PbO2It is placed in H3BO3It is impregnated in solution and removes ordered porous ZnO template
Obtain stainless steel base/nano array β-PbO2；Wherein H3BO3The concentration of solution is 0.25 mol/L；
(6) with the stainless steel base/nano array β-PbO of step (5)2For anode, stainless steel plate is cathode, in electroplate liquid, is adopted
With anodizing in stainless steel base/nano array β-PbO2Hole in electro-deposition nanometer β-PbO2Up to stainless base steel nanometer
Array β-PbO2Electrode；Wherein electroplate liquid is Pb (NO3)2-NaF-Cu(NO3)2Electroplate liquid, the pH value of electroplate liquid are 2；In electroplate liquid
Pb(NO3)2Concentration is 210.0 g/L, and NaF concentration is 0.8 g/L, Cu (NO3)2 Concentration is 30.0 g/L, anodizing
Temperature be 50 DEG C, DC current density 10mA/cm2, the DC electrodeposition time is 20min.
Pass through stainless steel base nano array β-PbO2The SEM figure (see figure 6) of electrode is it is found that made from through this embodiment not
Become rusty base steel nano-array β-PbO2Electrode material has the similar raised graininess knot of rule compared to embodiment 2 and embodiment 4
Structure, but dendroid is presented in structure.But its catalytically active surface product and common plane β-PbO2Electrode material, which compares, still to be increased,
Also the specific surface area of electrocatalytic reaction is effectively increased, to improve electrocatalysis characteristic；
The present embodiment stainless steel base plane β-PbO2Electrode and stainless steel base nano array β-PbO2The removal of electrode degrading phenol
Rate change with time figure as shown in fig. 7, degradation 90min after, the present embodiment stainless steel base nano array β-PbO2Electrode is to benzene
The removal rate of phenol is up to 80% ~ 85%；And common plane β-PbO2The removal rate of electrode Pyrogentisinic Acid is 65%；Common plane β-PbO2Electricity
The obvious low electrode material with the present embodiment of the catalytic efficiency of pole, the electrode of the present embodiment have biggish electro catalytic activity surface
Product；
The stainless steel base nano array β-PbO prepared under the conditions of different embodiments2The removal rate of electrode degrading phenol is at any time
Variation diagram is as shown in figure 8, as it can be observed in the picture that in polystyrene microsphere partial size appropriate, temperature appropriate and electro-deposition appropriate
The similar stainless steel base nano array β-PbO of pattern can be prepared under the conditions of time and current density etc.2Electrode material；No
Having with factors such as electrodeposition time and current densities on its pattern influences, and the time is too short to will lead to β-PbO2Lattice structure not at
Type, the time, the too long lattice structure that will lead to lost systematicness, but all had preferable catalytic action, made under the conditions of different embodiments
Standby β-PbO2Its catalytic activity of electrode material is compared with plane β-PbO2Electrode has promotion by a relatively large margin.
Claims (11)
1. a kind of using ordered porous ZnO as the stainless steel base nano array β-PbO of template2The preparation method of electrode, feature exist
In, the specific steps are as follows:
(1) using stainless steel plate as substrate, using liquid surface construction from part in stainless steel plate substrate self-assembled monolayer polystyrene
Microsphere template obtains stainless base steel/single layer polystyrene microsphere template；
(2) stainless base steel/single layer polystyrene microsphere template of step (1) is placed in precursor solution, using low-temperature hydrothermal
Legal system has sequence nano-ZnO template and obtains stainless base steel/single layer polystyrene microsphere/ordered nano ZnO template；Wherein presoma
Solution is ZnCl2Sodium citrate aqueous solution, the pH value of precursor solution are 10 ~ 11；
(3) using in organic solvent dissolution removal step (2) stainless base steel/single layer polystyrene microsphere/ordered nano ZnO template
Single layer polystyrene microsphere, and use H3BO3Solution carries out through-hole to the hole left after removal single layer polystyrene microsphere and obtains
To stainless base steel/porous nano ZnO template；Wherein organic solvent is toluene, methylene chloride, tetrahydrofuran or acetone；
(4) using stainless base steel/porous nano ZnO template of step (3) as anode, stainless steel plate is cathode, in electroplate liquid, is adopted
With anodizing in stainless base steel/porous nano ZnO template hole electro-deposition nanometer β-PbO2Obtain stainless base steel/more
Hole nano-ZnO/nano-array β-PbO2；
(5) by stainless base steel/porous nano ZnO/nanometer β-PbO2It is placed in H3BO3It is impregnated in solution and removes ordered porous ZnO template
Obtain stainless steel base/nano array β-PbO2；
(6) with the stainless steel base/nano array β-PbO of step (5)2For anode, stainless steel plate is cathode, in electroplate liquid, again
Using anodizing in stainless steel base/nano array β-PbO2Lattice structure on electro-deposition nanometer β-PbO2Up to stainless steel
Base nano array β-PbO2Electrode.
2. according to claim 1 using ordered porous ZnO as the stainless steel base nano array β-PbO of template2The preparation side of electrode
Method, it is characterised in that: step (1) stainless steel plate is to carry out pretreated activation stainless steel plate, wherein pretreatment includes stainless steel
Plate removes surface spikes, oxidation film through mechanical grinding, and oil removing is washed and is dried；Be subsequently placed in hydrochloric acid solution activation 5 ~
10 min are washed, are dried to obtain activation stainless steel plate.
3. according to claim 1 using ordered porous ZnO as the stainless steel base nano array β-PbO of template2The preparation side of electrode
Method, it is characterised in that: step (1) uses liquid surface construction from part self-assembled monolayer polystyrene microsphere in stainless steel plate substrate
The specific method of template is that monodisperse polystyrene microsphere stoste is added to dehydrated alcohol and carries out 1 ~ 5min of ultrasound to be gathered
Styrene/dehydrated alcohol mixed liquor drips polystyrene/dehydrated alcohol mixed liquor under the conditions of temperature is 20 ~ 30 DEG C dropwise
Enter to stand in deionized water and generate single layer polystyrene microsphere film, stainless steel base is inserted into deionization to be greater than 45° angle
In water, is taken out after single layer polystyrene microsphere is uniformly paved with stainless steel base and be dried to obtain stainless base steel/single layer polystyrene
Microsphere template；Wherein the concentration of monodisperse polystyrene microsphere stoste is 25 ~ 50 g/L, the partial size of monodisperse polystyrene microsphere
It is 5 ~ 10 μm；Monodisperse polystyrene microsphere stoste and the volume ratio of dehydrated alcohol are 4:(3 ~ 2).
4. according to claim 1 using ordered porous ZnO as the stainless steel base nano array β-PbO of template2The preparation side of electrode
Method, it is characterised in that: ZnCl in precursor solution in precursor solution in step (2)2Concentration is 0.1 ~ 0.3 mol/L, lemon
The concentration of sour sodium is 0.2 ~ 0.8 g/L.
5. according to claim 1 using ordered porous ZnO as the stainless steel base nano array β-PbO of template2The preparation side of electrode
Method, it is characterised in that: orderly nano-ZnO template is prepared using hydrothermal reaction at low temperature in step (2) and obtains stainless base steel/single layer polyphenyl
The specific steps are stainless steel plate/single layer polystyrene microsphere template is placed in presoma for ethylene microballoon/ordered nano ZnO template
In solution, incubation water heating reacts 1 ~ 5h under the conditions of temperature is 80 ~ 100 DEG C, takes out cooling, washes and be drying to obtain stainless steel
Base/single layer polystyrene microsphere/ordered nano ZnO template.
6. according to claim 1 using ordered porous ZnO as the stainless steel base nano array β-PbO of template2The preparation side of electrode
Method, it is characterised in that: H3BO3The concentration of solution is 0.05 ~ 0.50 mol/L.
7. according to claim 1 using ordered porous ZnO as the stainless steel base nano array β-PbO of template2The preparation side of electrode
Method, it is characterised in that: electroplate liquid is Pb (NO3)2-NaF-Cu(NO3)2Electroplate liquid, the pH value of electroplate liquid are 2 ~ 3.
8. according to claim 1 using ordered porous ZnO as the stainless steel base nano array β-PbO of template2The preparation side of electrode
Method, it is characterised in that: Pb (NO in electroplate liquid3)2Concentration is 190.0 ~ 210.0 g/L, and NaF concentration is 0.5 ~ 0.8 g/L, Cu
(NO3)2 Concentration is 15.0 ~ 30.0 g/L.
9. according to claim 1 using ordered porous ZnO as the stainless steel base nano array β-PbO of template2The preparation side of electrode
Method, it is characterised in that: the temperature of step (4) Anodic Oxidation method is 30 ~ 60 DEG C, and DC current density is 10 ~ 15mA/cm2,
The time of DC electrodeposition is 20 ~ 30min.
10. according to claim 1 using ordered porous ZnO as the stainless steel base nano array β-PbO of template2The preparation of electrode
Method, it is characterised in that: the temperature of step (6) Anodic Oxidation method is 30 ~ 60 DEG C, and DC current density is 10 ~ 15mA/
cm2, the time of DC electrodeposition is 10 ~ 30min.
11. using ordered porous ZnO as the stainless steel base nano array β-PbO of template described in any one of claim 1 ~ 102Electrode
Application of the electrode prepared by preparation method as aromatic hydrocarbon substance electrode in degradation industrial organic waste water.
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