CN113697908B - Preparation method of electrode for electrocatalytic degradation of printing and dyeing wastewater - Google Patents
Preparation method of electrode for electrocatalytic degradation of printing and dyeing wastewater Download PDFInfo
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- 230000015556 catabolic process Effects 0.000 title claims abstract description 23
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 23
- 239000002351 wastewater Substances 0.000 title claims abstract description 22
- 238000004043 dyeing Methods 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000010936 titanium Substances 0.000 claims abstract description 46
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 26
- 239000013543 active substance Substances 0.000 claims abstract description 15
- 150000002500 ions Chemical class 0.000 claims abstract description 9
- 239000002243 precursor Substances 0.000 claims abstract description 8
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 claims abstract description 7
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims abstract description 7
- GPRSOIDYHMXAGW-UHFFFAOYSA-N cyclopenta-1,3-diene cyclopentanecarboxylic acid iron Chemical compound [CH-]1[CH-][CH-][C-]([CH-]1)C(=O)O.[CH-]1C=CC=C1.[Fe] GPRSOIDYHMXAGW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000004528 spin coating Methods 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 4
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 claims abstract description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000002791 soaking Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 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 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 238000000137 annealing Methods 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 238000004544 sputter deposition Methods 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 5
- 239000011149 active material Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 239000002932 luster Substances 0.000 claims description 3
- 238000005498 polishing Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- ZDYUUBIMAGBMPY-UHFFFAOYSA-N oxalic acid;hydrate Chemical compound O.OC(=O)C(O)=O ZDYUUBIMAGBMPY-UHFFFAOYSA-N 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 9
- 239000010949 copper Substances 0.000 abstract description 8
- 238000003980 solgel method Methods 0.000 abstract description 3
- KHMOASUYFVRATF-UHFFFAOYSA-J tin(4+);tetrachloride;pentahydrate Chemical compound O.O.O.O.O.Cl[Sn](Cl)(Cl)Cl KHMOASUYFVRATF-UHFFFAOYSA-J 0.000 abstract description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract 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 10
- 229940012189 methyl orange Drugs 0.000 description 10
- 239000000758 substrate Substances 0.000 description 9
- 239000011734 sodium Substances 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000002071 nanotube Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 229910006404 SnO 2 Inorganic materials 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000000987 azo dye Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000010840 domestic wastewater Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Images
Classifications
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- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/843—Arsenic, antimony or bismuth
- B01J23/8435—Antimony
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- 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
- C02F2101/34—Organic compounds containing oxygen
-
- 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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of an electrode for electrocatalytic degradation of printing and dyeing wastewater, which comprises the following steps: preparation of Ti/TiO 2 NTs/Pt in Ti/TiO 2 -NTs/Pt surface spin-coating active substance sol, wherein the preparation method of the active substance sol comprises the following steps: stirring the ethylene glycol solution and the citric acid water bath to prepare a precursor; and sequentially adding tin chloride pentahydrate, antimony chloride, copper nitrate trihydrate and ferrocenecarboxylic acid into the precursor, and dissolving to obtain the active substance sol. The invention is realized by adding the titanium oxide into TiO 2 A Pt layer is sputtered on the surface of NTs through ions to increase the conductivity and stability of the Pt layer, and Sn is prepared through a sol-gel method 9 Sb 1 Cu 1 Fe 0.1 O 21.65 The active layer improves the electrocatalytic degradation performance of the electrode.
Description
Technical Field
The invention relates to the field of printing and dyeing wastewater treatment, in particular to a preparation method of an electrode for electrocatalytic degradation of printing and dyeing wastewater.
Background
With the increasing frequency of activities of industry, agriculture and city, human beings, water pollution becomes one of the main problems of environmental pollution in the world, wherein the refractory organic wastewater is the key point of treatment, and comprises coking wastewater, paper-making wastewater, pharmaceutical wastewater, printing and dyeing wastewater, domestic wastewater, agricultural wastewater and the like. The printing and dyeing wastewater is widely concerned due to the characteristics of high chromaticity, difficult degradation, large environmental hazard, wide dispersion of production sites, difficult centralized treatment and the like. The printing and dyeing wastewater mainly contains pollutants such as azo dyes, fluorescent whitening agents, polyvinyl alcohol and polypropylene sizing agents, nitrogen-containing bleaching agents, aromatic amine dyes and the like, wherein the azo dyes are the most common printing and dyeing dyes, and the composition analysis of the printing and dyeing wastewater discharged in the manufacturing industry of textile, clothing, shoes and hats in Dongguan city is combined, so that the azo dye wastewater occupies more than 60% of the total printing and dyeing wastewater discharged in Dongguan city at present.
The non-biochemical degradation organic pollutants can be degraded into the biochemical degradation compounds by electrochemically catalyzing and degrading the printing and dyeing wastewater, so that the biological treatment efficiency is improved; by electrochemical catalytic deep oxidation (electrochemical incineration), the organic pollutants in the wastewater are completely mineralized to generate dehydrogenated or dehydroxylated derivatives, and the dehydrogenated or dehydroxylated derivatives are finally converted into CO 2 And H 2 And O. At present, electrodes for electrocatalytic degradation of printing and dyeing wastewater mainly include a Dimensionally Stable Anode (DSA), a boron-doped diamond electrode (BDD), a Reactive Electrochemical Membrane (REM), and the like, wherein the DSA electrode is an electrode material which takes metallic titanium as a substrate and is coated with other metallic oxides on the surface thereof, and a common DSA electrode at present is Ti/RuO 2 、Ti/SnO 2 And Ti/IrO 2 Isoelectrodes of Ti/SnO 2 The modified DSA electrode has low cost and stable catalytic performance, and is widely used for degrading organic matters through electrocatalysis. But Ti/SnO 2 The electrocatalytic efficiency and lifetime of type DSA electrodes are yet to be further improved.
Disclosure of Invention
In order to further promote Ti/SnO 2 Compared with the prior art, the electrode has higher electrocatalytic degradation efficiency, stability and service life.
Specifically, the technical scheme adopted by the invention is as follows:
a preparation method of a DSA electrode for electrocatalytic degradation of printing and dyeing wastewater comprises the following steps:
s1, preparing Ti/TiO 2 -NTs/Pt；
S2 in Ti/TiO 2 -NTs/Pt surfaceSpin coating active substance sol, wherein the preparation method of the active substance sol comprises the following steps:
s21, stirring the ethylene glycol solution and the citric acid water bath to prepare a precursor;
s22, adding stannic chloride pentahydrate, antimony chloride, copper nitrate trihydrate and ferrocenecarboxylic acid into the precursor in sequence, and dissolving to obtain the active substance sol.
Preferably, the molar ratio of ethylene glycol, citric acid, stannic chloride pentahydrate, antimony chloride, copper nitrate trihydrate and ferrocenecarboxylic acid is 70:15:9:1:1:0.1 or 65:22:9:1:1:0.1 or 55:30:9:1:1:0.1.
preferably in Ti/TiO 2 The method for spin-coating the active substance sol on the NTs/Pt surface specifically comprises the following steps:
s31, dripping the active material sol into the rotating Ti/TiO 2 -NTs/Pt surface;
s32, after coating, putting the coating into an oven to bake for 5-100 minutes at the temperature of 80-150 ℃, then putting the coating into a muffle furnace to perform heat treatment for 1-30 minutes at the temperature of 250-700 ℃, and cooling to room temperature;
and S32, repeating the steps S31 and S32 for multiple times.
Preferably, ti/TiO 2 The preparation method of the NTs/Pt comprises the following steps:
s41, pretreating a Ti sheet;
s42, putting a Ti sheet serving as an anode and a platinum wire serving as a cathode into an electrolyte mixed with ethylene glycol, water and ammonium fluoride for oxidation, wherein the voltage is 5-50V, the electrode gap is 2-5 cm, and the oxidation time is 1-24 hours;
s43, soaking in absolute ethyl alcohol for 0.5-2 hours, and further performing ultrasonic treatment on the ethanol for 10-500 seconds;
s44, annealing and crystallizing, and annealing for 1-8 hours at 260-720 ℃ in an air atmosphere;
s45, mixing TiO 2 Ion sputtering NTs under a Pt ion sputtering apparatus for 10-500 seconds, vacuum drying at room temperature.
Preferably, the Ti sheet pretreatment specifically includes:
s51, polishing the pure titanium sheet to be metallic luster by using sand paper;
s52, performing ultrasonic treatment on acetone for 0.5 to 2 hours, soaking in 0.5 to 1.3M NaOH aqueous solution at 60 to 90 ℃ for 1 to 3 hours, and cleaning;
s53, soaking in 10% oxalic acid water solution at 60-90 ℃ for 2-5 hours;
s54, ultrasonically cleaning the mixture for 0.2 to 1 hour by using deionized water, and storing the mixture in absolute ethyl alcohol.
Preferably, the volume ratio of ethylene glycol, water and ammonium fluoride is 5.
The invention grows TiO with larger specific surface on the titanium substrate 2 Nanotube bundle (TiO) 2 NTs) to increase the binding capacity of the substrate to the active layer by its regular nanostructure and large specific surface, then on TiO 2 A Pt layer is sputtered on the surface of NTs through ions to increase the conductivity and stability of the Pt layer, and Sn is prepared through a sol-gel method 9 Sb 1 Cu 1 Fe 0.1 O 21.65 The active layer improves the electrocatalytic degradation performance of the electrode.
Drawings
FIG. 1 is a schematic view of an electrode according to an embodiment of the present invention;
FIG. 2 is a flow chart of a method for manufacturing an electrode according to an embodiment of the present invention;
FIG. 3 is a schematic representation of an embodiment of the present invention showing Ti/TiO material 2 -NTs（a）、A 0 SEM images of electrode (b) and electrode (c);
FIG. 4 shows an electrode A and an electrode A in accordance with an embodiment of the present invention 0 Electrodes are respectively on 1M Na 2 SO 4 CV plot in electrolyte;
FIG. 5 shows the electrode A and the electrode A without organic methyl orange in one embodiment of the present invention 0 Electrodes are respectively on 1M Na 2 SO 4 LSV profile in electrolyte;
FIG. 6 shows an electrode A and an electrode A when organic methyl orange is contained in an embodiment of the present invention 0 Electrode at 1M Na 2 SO 4 LSV profile in electrolyte;
FIG. 7 shows an electrode A and an electrode A in accordance with an embodiment of the present invention 0 Electrodes are respectively on 1M Na 2 SO 4 0.1A/cm in electrolyte 2 An accelerated life comparison plot at current density;
FIG. 8 shows the present inventionIn one embodiment, electrode A and electrode A 0 Graph of electrocatalytic degradation of electrode to methyl orange.
Detailed Description
The invention provides a preparation method of a DSA electrode for electrocatalytic degradation of printing and dyeing wastewater, which is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
As shown in fig. 1 and 2, the invention provides a preparation method of a DSA electrode for electrocatalytic degradation of printing and dyeing wastewater, comprising the following steps:
s1, preparing Ti/TiO 2 -NTs/Pt；
S2 in Ti/TiO 2 -coating active substance sol on the surface of NTs/Pt by spinning, wherein the preparation method of the active substance sol comprises the following steps:
s21, adding ethylene glycol ((CH) 2 OH) 2 ) Solution and citric acid (C) 6 H 8 O 7 ·H 2 O) stirring in water bath to prepare a precursor;
s22, adding tin chloride pentahydrate (SnCl) into the precursor in sequence 4 ·5H 2 O), antimony chloride (SbCl) 3 ) Copper nitrate trihydrate (Cu (NO) 3 ) 2 ·3H 2 O) and ferrocenecarboxylic acid (C) 11 H 10 FeO 2 ) Dissolving to obtain the active material sol Sn 9 Sb 1 Cu 1 Fe 0.1 O 21.65 。
Preferably, the molar ratio of ethylene glycol, citric acid, stannic chloride pentahydrate, antimony chloride, copper nitrate trihydrate and ferrocenecarboxylic acid is 70:15:9:1:1:0.1 or 65:22:9:1:1:0.1 or 55:30:9:1:1:0.1.
preferably, in Ti/TiO 2 The method for spin-coating the active substance sol on the NTs/Pt surface specifically comprises the following steps:
s31, dripping the active material sol into the rotating Ti/TiO 2 -NTs/Pt surface;
s32, after coating, putting the coated film into an oven to be baked for 5-100 minutes at the temperature of 80-150 ℃, then putting the film into a muffle furnace to be thermally treated for 1-30 minutes at the temperature of 250-700 ℃, and cooling the film to room temperature;
and S32, repeating the steps S31 and S32 for multiple times.
Preferably, ti/TiO 2 The preparation method of NTs/Pt comprises the following steps:
s41, pretreating a Ti sheet;
s42, taking a Ti sheet as an anode and a platinum wire as a cathode, and adding ethylene glycol, water and ammonium fluoride (NH) 4 F) Oxidizing in the mixed electrolyte, wherein the voltage is 5-50V, the electrode gap is 2-5 cm, and the oxidizing time is 1-24 hours;
s43, adding absolute ethyl alcohol (C) 2 H 6 O) soaking for 0.5-2 hours, and further performing ultrasonic treatment on the mixture for 10-500 seconds by using ethanol;
s44, annealing and crystallizing, and annealing for 1-8 hours at 260-720 ℃ in an air atmosphere;
s45, preparing TiO from 2 Ion sputtering NTs under a Pt ion sputtering apparatus for 10-500 seconds, vacuum drying at room temperature.
Preferably, the Ti sheet pretreatment specifically comprises:
s51, polishing the pure titanium sheet to be metallic luster by using abrasive paper;
s52, performing ultrasonic treatment on acetone for 0.5 to 2 hours, soaking in 0.5 to 1.3M sodium hydroxide (NaOH) aqueous solution at the temperature of between 60 and 90 ℃ for 1 to 3 hours, and cleaning;
s53, adding 10% oxalic acid (C) 2 H 2 O 4 ·2H 2 O) soaking in water solution at 60-90 deg.c for 2-5 hr;
s54, ultrasonically cleaning the mixture for 0.2 to 1 hour by using deionized water, and storing the mixture in absolute ethyl alcohol.
Preferably, the volume ratio of ethylene glycol, water and ammonium fluoride is 5.
In order to verify the electrochemical performance of the electrode material of the present invention, the electrode of the present invention is hereinafter named Ti/TiO 2 -NTs/Pt/Sn 9 Sb 1 Cu 1 Fe 0.1 O 21.65 An electrode, referred to as A electrode, in which Ti is a titanium plate substrate and TiO 2 NTs is titanium dioxide nanotubes, pt is a platinum nanolayer, sn 9 Sb 1 Cu 1 Fe 0.1 O 21.65 Is an active substance. Selecting Ti/TiO 2 -NTs/Sn 9 Sb 1 O 20.5 Electrode as reference electrode, abbreviated as A 0 Electrode of Ti/TiO 2 -NTs/Sn 9 Sb 1 O 20.5 The electrode was prepared in a similar manner to electrode a described above.
FIG. 3 shows Ti/TiO 2 -NTs（a）、A 0 SEM images of the electrode (b) and the electrode A (c), and Scanning Electron Microscopy (SEM) was performed using a scanning electron microscope of JSM-6701F, japan Electron Co. Observation of Ti/TiO with 30000 times objective lens 2 NTs/Pt substrate and observing the topography change of the electrode surface with 1500 times objective lens. As can be seen from FIG. 3 (a), the titanium dioxide nanotube array grown on the Ti sheet has good uniformity, the tubes are tightly combined with each other, and the diameters of the tubes are uniform and about 80-100nm. In the figure, 3 (b) is A 0 Referring to the electrode, the active layer can be well attached to the titanium dioxide nanotube with clear layers. Fig. 3 (c) is an a electrode in which the active layer is well attached to the titanium dioxide nanotube and has a certain crystal arrangement structure.
Counter electrode A and reference A 0 The voltammetric linear scan curve of the electrode is compared, FIG. 4 is the CV curve of the potential window from-1.2V to 1.2V at the scan rate of 0.03V/s, and it can be seen from FIG. 4 and the reference A 0 Compared with the electrode, the oxidation reduction peak of the electrode A is obviously improved.
Further comparison of electrode A and reference A 0 The oxygen evolution potential of the electrodes, linear voltammetric scan curves for both electrodes, FIG. 5 is 1M Na in the absence of organic methyl orange 2 SO 4 LSV curve in the electrolyte, from which we can see, reference A 0 The Oxygen Evolution Potential (OEP) of the electrode was 1.5V and the Oxygen Evolution Potential (OEP) of the a electrode was 1.7V, with higher oxygen evolution potentials indicating a more difficult occurrence of oxygen evolution side reactions, thereby increasing the faraday efficiency of the electrode. FIG. 6 shows the reaction of 1M Na in an organic substance containing methyl orange 2 SO 4 The LSV curve in the electrolyte can be seen from the graph, and the degradation peak potential ratio of the electrode A to methyl orange is referred to the A 0 The electrode is 0.3V lower and the peak current is higher than the latter,the result shows that the A electrode is easier to degrade methyl orange organic matters and higher in efficiency after the Pt layer and the modified active layer are introduced.
Comparative electrode A and reference A 0 Electrode Life, accelerated Life test was performed on both electrodes, FIG. 7 is in 1M Na 2 SO 4 0.1A/cm is added into the electrolyte 2 And (3) the current density is the electrode deactivation when the electrode voltage exceeds the initial voltage by 5V. As can be seen from FIG. 7, reference A 0 The service life of the electrode is 4200s (70 min), the service life of the electrode A is 6800s (113 min), namely after the Pt layer and the modified active layer are introduced, the service life of the electrode is prolonged by 43min, and the service life is greatly improved. The introduction of the Pt layer is beneficial to isolating strong oxidizing radicals in the electrolyte to protect the Ti substrate from being corroded, meanwhile, the conductivity of the substrate and the active layer is improved, and the introduction of elements such as copper and iron also synergistically improves the service life and stability of the electrode.
Electrode A and reference A 0 The electrocatalytic degradation curves of the electrodes on methyl orange are shown in FIG. 8, and the degradation conditions are 50mg/L of 1M Na of methyl orange 2 SO 4 Electrolyte solution with current density of 30mA/cm 2 . As can be seen from FIG. 8, the degradation amounts at 30 minutes were 52% and 80%, respectively, and the degradation amounts at 60 minutes were 83% and 96%, respectively, as compared with reference A 0 Compared with the electrode, the electrode A has higher efficient electrocatalytic degradation capability on methyl orange.
In conclusion, the invention prepares a novel DSA electrode by TiO 2 Regular nanostructure of NTs, increase of the specific surface of the Ti plate, increase of the binding capacity of the Ti substrate to the active layer, and subsequent formation of the active layer on the TiO substrate 2 A Pt layer is sputtered on the surface of NTs through ions to increase the conductivity and stability of the Pt layer, and further Sn is prepared through a sol-gel method 9 Sb 1 Cu 1 Fe 0.1 O 21.65 The active layer improves the electrocatalytic degradation performance of the electrode.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (4)
1. A preparation method of an electrode for electrocatalytic degradation of printing and dyeing wastewater is characterized by comprising the following steps:
s1, preparing Ti/TiO 2 -NTs/Pt；
S2 in Ti/TiO 2 -NTs/Pt surface spin-coating active substance sol, wherein the preparation method of the active substance sol comprises the following steps:
s21, stirring the ethylene glycol solution and the citric acid water bath to prepare a precursor;
s22, adding stannic chloride pentahydrate, antimony chloride, copper nitrate trihydrate and ferrocenecarboxylic acid into the precursor in sequence, and dissolving to obtain the active substance sol, wherein the molar ratio of ethylene glycol, citric acid, stannic chloride pentahydrate, antimony chloride, copper nitrate trihydrate and ferrocenecarboxylic acid is 70:15:9:1:1:0.1 or 65:22:9:1:1:0.1 or 55:30:9:1:1:0.1;
wherein, ti/TiO 2 The preparation method of NTs/Pt comprises the following steps:
s41, pretreating a Ti sheet;
s42, putting a Ti sheet serving as an anode and a platinum wire serving as a cathode into an electrolyte mixed with ethylene glycol, water and ammonium fluoride for oxidation, wherein the voltage is 5-50V, the electrode gap is 2-5 cm, and the oxidation time is 1-24 hours;
s43, soaking in absolute ethyl alcohol for 0.5-2 hours, and further performing ultrasonic treatment on the ethanol for 10-500 seconds;
s44, annealing and crystallizing, and annealing for 1-8 hours at 260-720 ℃ in an air atmosphere;
s45, mixing TiO 2 Ion sputtering NTs under a Pt ion sputtering apparatus for 10-500 seconds, vacuum drying at room temperature.
2. The method of claim 1, wherein the Ti/TiO is added 2 The method for spin-coating the active substance sol on the NTs/Pt surface specifically comprises the following steps:
s31, dripping the active material sol into the rotating Ti/TiO 2 -NTs/Pt surface;
s32, after coating, putting the coated film into an oven to be baked for 5-100 minutes at the temperature of 80-150 ℃, then putting the film into a muffle furnace to be thermally treated for 1-30 minutes at the temperature of 250-700 ℃, and cooling the film to room temperature;
s32, repeating the steps S31 and S32 for multiple times.
3. The method according to claim 1, wherein the Ti sheet pretreatment specifically comprises:
s51, polishing the pure titanium sheet to be metallic luster by using abrasive paper;
s52, performing ultrasonic treatment on acetone for 0.5 to 2 hours, soaking in 0.5 to 1.3M NaOH aqueous solution at 60 to 90 ℃ for 1 to 3 hours, and cleaning;
s53, soaking in 10% oxalic acid water solution at 60-90 ℃ for 2-5 hours;
s54, ultrasonically cleaning the mixture for 0.2 to 1 hour by using deionized water, and storing the mixture in absolute ethyl alcohol.
4. The preparation method according to claim 1, wherein the volume ratio of ethylene glycol, water and ammonium fluoride in the mixed electrolyte is 5.
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