CN115259295A - Electrode manufacturing method for degrading resorcinol by electrocatalysis, product and application - Google Patents
Electrode manufacturing method for degrading resorcinol by electrocatalysis, product and application Download PDFInfo
- Publication number
- CN115259295A CN115259295A CN202210969254.9A CN202210969254A CN115259295A CN 115259295 A CN115259295 A CN 115259295A CN 202210969254 A CN202210969254 A CN 202210969254A CN 115259295 A CN115259295 A CN 115259295A
- Authority
- CN
- China
- Prior art keywords
- electrode
- solution
- tungsten
- antimony
- titanium sheet
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 230000000593 degrading effect Effects 0.000 title description 7
- 239000000243 solution Substances 0.000 claims abstract description 107
- 239000010936 titanium Substances 0.000 claims abstract description 102
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 76
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 76
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 64
- 239000002243 precursor Substances 0.000 claims abstract description 57
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 52
- 239000010937 tungsten Substances 0.000 claims abstract description 47
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 46
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 28
- 229910006404 SnO 2 Inorganic materials 0.000 claims abstract description 27
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 230000015556 catabolic process Effects 0.000 claims abstract description 22
- 238000006731 degradation reaction Methods 0.000 claims abstract description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000004070 electrodeposition Methods 0.000 claims abstract description 17
- 239000000758 substrate Substances 0.000 claims abstract description 15
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 5
- 238000005979 thermal decomposition reaction Methods 0.000 claims abstract description 5
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 48
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 238000002791 soaking Methods 0.000 claims description 27
- 238000005303 weighing Methods 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 150000001462 antimony Chemical class 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- KXWBWCWPLXBJAN-UHFFFAOYSA-N [Sb].[W] Chemical compound [Sb].[W] KXWBWCWPLXBJAN-UHFFFAOYSA-N 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 3
- 239000011241 protective layer Substances 0.000 claims description 3
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 4
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 239000007772 electrode material Substances 0.000 abstract description 3
- 229910052759 nickel Inorganic materials 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 238000012546 transfer Methods 0.000 abstract description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract 2
- 229910052697 platinum Inorganic materials 0.000 abstract 1
- -1 tungsten co-modified tin dioxide Chemical class 0.000 abstract 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000006056 electrooxidation reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 206010043275 Teratogenicity Diseases 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005842 biochemical reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- KSGNWFFQNWVFQW-UHFFFAOYSA-N cyclohexa-3,5-diene-1,3-diol Chemical compound OC1CC(O)=CC=C1 KSGNWFFQNWVFQW-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 231100000211 teratogenicity Toxicity 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment 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
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- C02F2101/345—Phenols
Abstract
The invention discloses a method for manufacturing an electrode for electrocatalytic degradation of resorcinol, a product and application thereof, which comprises the steps of pretreating a titanium sheet, preparing a precursor solution containing antimony (Sb), tin (Sn) and tungsten (W), and preparing antimony and tungsten co-modified tin dioxide (Sb-SnO) on the surface of the titanium sheet by using the titanium sheet as a substrate and utilizing a thermal decomposition method 2 ) Obtaining Ti/W, sb-SnO as electrode material 2 And an electrode. By adopting a constant current method and using Ti/W, sb-SnO 2 A working electrode, a platinum sheet as a counter electrode, nickel nitrate (Ni (NO) 3 ) 2 ) The solution is electrolyte solution, and electrochemical deposition is carried out to obtain Ti/W, sb-SnO modified by nickel 2 And an electrode. Since the nickel-based material hasWith strong electron transmission capability, niO or Ni (OH) 2 And W, sb-SnO 2 The electrode is compounded, and the charge transfer capacity of the surface of the electrode is effectively improved. On the other hand, snO codoped with tungsten and antimony 2 Then, the activity of the electrode is effectively improved.
Description
Technical Field
The invention belongs to the technical field of catalytic environmental protection, and particularly relates to a manufacturing method of an electrode for degrading resorcinol by electrocatalysis, a product and an application.
Background
High concentration organic pollutants and harmful pollutants discharged in industrial production cause great harm to human health and environment. In particular, the benzene-containing cyclic compound is difficult to degrade and has an inhibitory or toxic effect on biochemical reactions. Resorcinol is used in the dye industry, plastics industry, medicine, rubber, etc. It is very difficult to treat such waste water by conventional methods because of its high toxicity and teratogenicity, which may cause damage to human health and ecological environment. Therefore, the development of a rapid and efficient phenol degradation method is urgently needed. The electrochemical oxidation has the advantages of mild reaction conditions, environmental friendliness, strong oxidation capacity and the like, and is a hotspot of current research. Electrochemical oxidation is therefore considered a promising wastewater treatment technology and has attracted considerable attention in water treatment research.
Ti/SnO 2 The electrode has high oxygen evolution potential and electrocatalytic activity, so that the electrode is widely researched in the field of electrochemical catalysis, but the electrode still has the problems of short service life, low oxidation capacity and the like, and practical application is limited. Researches find that doping is one of effective means for modifying electrode materials, and proper doping can effectively improve the electron transmission rate of the electrode and promote the surface diffusion of ions, thereby effectively improving the catalytic oxidation capability of the electrode. On the other hand, the stability of the electrode can be improved by constructing the protective layer, so that the purpose of prolonging the service life of the electrode is achieved.
Disclosure of Invention
In order to realize the efficient removal of resorcinol, the invention aims to provide a method for manufacturing a high-performance electrode for electrically catalyzing and degrading resorcinol.
Yet another object of the present invention is to: provides a high-performance electrode product for the electrocatalytic degradation of resorcinol prepared by the method.
Yet another object of the present invention is to: provides an application of the product.
The purpose of the invention is realized by the following scheme: a method for manufacturing an electrode for the electrocatalytic degradation of resorcinol, the method comprising:
(1) Pretreating a titanium sheet (the thickness is 0.1 to 0.2 mm, and the size is 2 multiplied by 3 cm);
(2) Preparing a precursor solution containing antimony (Sb), tin (Sn) and tungsten (W);
(3) Preparing antimony and tungsten co-doped tin dioxide (SnO) on the surface of a titanium sheet by using the titanium sheet as a substrate and adopting a thermal decomposition method 2 ) Catalyst to obtain Ti/Sb, W-SnO 2 An electrode;
(4) With Ti/Sb, W-SnO 2 A working electrode, a Pt sheet as a counter electrode, and nickel nitrate (Ni (NO) 3 ) 2 ) The solution is electrolyte solution, and electrochemical deposition is carried out by adopting a constant current method to obtain the nickel-modified antimony and tungsten co-doped tin dioxide/titanium plate electrode.
The pretreatment titanium sheet comprises:
(1) Soaking the titanium sheet in a 40% sodium hydroxide solution, and keeping the temperature at 70-90 ℃ for 0.5-1h;
(2) Soaking the titanium sheet obtained in the step (1) in 6M HCl, and reacting at 80-90 ℃ for 1-2h;
(3) Washing the titanium sheet obtained in the step (2) with deionized water for several times, and finally soaking in absolute ethyl alcohol for later use.
The Ti/Sb, W-SnO 2 The preparation of the electrode comprises:
(1) Respectively preparing SnCl with the concentration of 1mol/L 4 ˙5H 2 O n-Butanol solution, 1mol/L SbCl 3 N-butanol solution, 1mol/L SnCl 4 ˙5H 2 O n-butanol solution, 1mol/L WCl 6 Ethanol solution;
(2) Taking appropriate amount of the three solutions in the step (1) according to the doping ratio of antimony and tungsten, and carrying out ultrasonic treatment for 5 min to uniformly mix the three solutions;
(3) Uniformly coating 200 mu l of the mixed solution in the step (2) on a titanium sheet, and standing at room temperature for 1h;
(4) And (4) placing the titanium sheet obtained in the step (3) in a muffle furnace to roast at 550 ℃ for 2h, and controlling the heating rate to be 3 ℃/min. Finally naturally cooling to room temperature to obtain Ti/Sb, W-SnO 2 And an electrode.
The doping proportion of antimony is 2% -5%, and the doping proportion of tungsten is 2% -5%. The concentration of the nickel nitrate is 0.1 to 0.5 mol/L, the constant current is-1 to-5 mA, and the electrodeposition time is 5 to 30min.
The invention provides an electrode for degrading resorcinol by electrocatalysis, which is prepared by any one of the methods, and specifically comprises the following steps: a titanium sheet substrate; the titanium sheet substrate is covered with an antimony-tungsten co-doped tin dioxide catalyst; and a nickel hydroxide or nickel oxide protective layer is deposited on the surface of the antimony-tungsten co-doped stannic oxide catalyst.
The invention provides a nickel-modified Ti/Sb, W-SnO 2 The application of the electrode for electrocatalytic degradation of resorcinol at normal temperature.
The preparation of the tungsten and antimony co-doped tin dioxide/titanium plate electrode comprises the following steps:
(3-1) according to the doping proportion of tungsten and antimony, taking a proper amount of precursor solution and uniformly mixing;
(3-2) uniformly coating 200 mu l of the mixed solution in the step (3-1) on a titanium sheet, and standing at room temperature for 1h;
and (3-3) placing the titanium sheet prepared in the step (3-2) in a muffle furnace to be roasted for 2h at the temperature of 550 ℃, and controlling the heating rate to be 3 ℃/min. And finally, naturally cooling to room temperature to obtain the tungsten and antimony co-doped tin dioxide/titanium plate electrode.
The invention provides a method for manufacturing a high-performance electrode for electrically catalyzing and degrading resorcinol. The electrode takes a titanium sheet as a substrate and Sb, W-SnO 2 NiO or Ni (OH) 2 The composite material is an electrode material and shows higher activity and stability for electrochemically degrading resorcinol. On the one hand, because the nickel-based material has stronger electron transmission capacity, niO or Ni (OH) 2 And W, sb-SnO 2 The electrode is compounded, and the charge transfer capacity of the surface of the electrode is effectively improved. On the other hand, snO codoped with tungsten and antimony 2 And then, the activity of the electrode is effectively improved.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will aid those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any manner. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
An electrode for the electrocatalytic degradation of resorcinol, which is manufactured by the following steps:
(1) Pre-treating a titanium sheet:
soaking a titanium sheet with the thickness of 0.1mm and the size of 2 multiplied by 3 cm in 40 percent sodium hydroxide solution, and keeping the titanium sheet at 80 ℃ for 1h; then soaking the mixture in 6M HCl, and reacting for 2 hours at 90 ℃; taking out, washing with deionized water for several times, and soaking in anhydrous ethanol for use;
(2) Preparing precursor solution containing antimony (Sb), tin (Sn) and tungsten (W)
Weighing SnCl 4 ˙5H 2 O1.75 g is dissolved in 5ml of n-butanol solution as a tin-containing precursor solution; weighing SbCl 3 1.15g of antimony-containing precursor solution was dissolved in 5ml of n-butanol solution; weighing WCl 6 1.98g of the precursor solution is dissolved in 5ml of ethanol solution to be used as a precursor solution containing tungsten;
(3) Taking a titanium sheet as a substrate, uniformly mixing 900 mu l of tin-containing precursor solution, 50 mu l of antimony-containing precursor solution and 50 mu l of tungsten-containing precursor solution, uniformly coating 200 mu l of the mixed solution on the titanium sheet obtained in the step (1), standing at room temperature for 1h, then roasting in a muffle furnace at 550 ℃ for 2h, controlling the heating rate to be 3 ℃/min, and finally naturally cooling to room temperature to obtain the tungsten and antimony co-doped tin dioxide/titanium sheet electrode to obtain Ti/Sb, W-SnO 2 An electrode;
(4) With Ti/Sb, W-SnO 2 As working electrode, pt sheet as counter electrode, with 50ml 0.1M nickel nitrate Ni (NO) 3 ) 2 And performing electrochemical deposition by adopting a constant current method with constant current of-1 mA and electro-deposition time of 0.5 h to obtain the nickel-modified antimony and tungsten co-doped tin dioxide/titanium plate electrode.
The electrode is taken as a working electrode, a Pt sheet is taken as a counter electrode, ag/AgCl is taken as a reference electrode, 50ml of 100mg/L resorcinol is taken as a solution to be degraded, 0.71g of anhydrous sodium sulfate containing electrolyte, and the 2h resorcinol degradation rate is 100% under the voltage of 3V.
Example 2
An electrode for the electrocatalytic degradation of resorcinol, which is manufactured by the following steps:
(1) Pretreating a titanium sheet with the thickness of 0.1mm and the size of 2 multiplied by 3 cm:
soaking a titanium sheet (with the thickness of 0.1mm and the size of 2 multiplied by 3 cm) in 40 percent sodium hydroxide solution, and keeping the temperature at 80 ℃ for 1 hour; then soaking the mixture in 6M HCl, and reacting for 2 hours at 90 ℃; taking out, washing with deionized water for several times, and soaking in anhydrous ethanol for use;
(2) Preparing a precursor solution containing antimony (Sb), tin (Sn) and tungsten (W):
weighing SnCl 4 ˙5H 2 O1.75 g was dissolved in 5ml of n-butanol solution as a tin-containing precursor solution, and SbCl was weighed 3 1.15g of antimony-containing precursor solution was dissolved in 5ml of n-butanol solution, and WCl was weighed 6 1.98g of the precursor solution is dissolved in 5ml of ethanol solution to be used as a precursor solution containing tungsten;
(3) Uniformly mixing 925 mu l of tin-containing precursor solution, 25 mu l of antimony-containing precursor solution and 50 mu l of tungsten-containing precursor solution, uniformly coating 200 mu l of the mixed solution on a titanium sheet, standing at room temperature for 1h, placing the titanium sheet as a substrate in a muffle furnace for roasting at 550 ℃ for 2h, controlling the heating rate to be 3 ℃/min, and naturally cooling to room temperature to obtain the antimony-tungsten co-doped tin dioxide SnO 2 Catalyst to obtain Ti/Sb, W-SnO 2 An electrode;
(4) With Ti/Sb, W-SnO 2 As working electrode, pt sheet as counter electrode, with 50ml 0.1M nickel nitrate Ni (NO) 3 ) 2 And performing electrochemical deposition by adopting a constant current method with constant current of-1 mA and electro-deposition time of 0.5 h to obtain the nickel-modified antimony and tungsten co-doped tin dioxide/titanium plate electrode.
The electrode is taken as a working electrode, a Pt sheet is taken as a counter electrode, ag/AgCl is taken as a reference electrode, 50ml of 100mg/L resorcinol is taken as a solution to be degraded, 0.71g of anhydrous sodium sulfate containing electrolyte, and the 2-hour resorcinol degradation rate is 90% under the voltage of 3V.
Example 3
An electrode for the electrocatalytic degradation of resorcinol, which is prepared by the following method:
(1) Pretreating a titanium sheet with the thickness of 0.1mm and the size of 2 multiplied by 3 cm:
soaking a titanium sheet (with the thickness of 0.1mm and the size of 2 multiplied by 3 cm) in 40 percent sodium hydroxide solution, and keeping the temperature at 80 ℃ for 1 hour; then soaking the mixture in 6M HCl, and reacting for 2 hours at 90 ℃; taking out, washing with deionized water for several times, and soaking in anhydrous ethanol for use;
(2) Preparing a precursor solution containing antimony (Sb), tin (Sn) and tungsten (W):
weighing SnCl 4 ˙5H 2 O1.75 g was dissolved in 5ml of n-butanol solution as a tin-containing precursor solution, and SbCl was weighed 3 1.15g of antimony-containing precursor solution was dissolved in 5ml of n-butanol solution, and WCl was weighed 6 1.98g of the precursor solution is dissolved in 5ml of ethanol solution to be used as a precursor solution containing tungsten;
(3) Uniformly mixing 950 mul of tin-containing precursor solution, 25 mul of antimony-containing precursor solution and 25 mul of tungsten-containing precursor solution, uniformly coating 200 mul of the mixed solution on a titanium sheet, taking the titanium sheet as a substrate, standing at room temperature for 1h, then placing the titanium sheet in a muffle furnace for roasting at 550 ℃ for 2h, controlling the heating rate to be 3 ℃/min, and preparing antimony and tungsten co-doped tin dioxide SnO on the surface of the titanium sheet by adopting a thermal decomposition method 2 Catalyst to obtain Ti/Sb, W-SnO 2 An electrode;
(4) With Ti/Sb, W-SnO 2 As working electrode, pt sheet as counter electrode, with 50ml 0.1M nickel nitrate Ni (NO) 3 ) 2 The solution is electrolyte solution, electrochemical deposition is carried out by adopting a constant current method, the constant current is-1 mA, and the electrodeposition time is 0.5 h, so that the nickel-modified antimony and tungsten co-doped tin dioxide/titanium plate electrode is obtained.
The electrode is taken as a working electrode, a Pt sheet is taken as a counter electrode, ag/AgCl is taken as a reference electrode, 50ml of 100mg/L resorcinol is taken as a solution to be degraded, 0.71g of anhydrous sodium sulfate containing electrolyte, and the 2-hour resorcinol degradation rate is 90% under the voltage of 3V.
Comparative example
An antimony-doped tin dioxide/titanium plate electrode for electrocatalytic degradation of resorcinol is prepared by the following steps:
(1) Pretreating a titanium sheet with the thickness of 0.2 mm and the size of 2 multiplied by 3 cm:
soaking titanium sheet (thickness 0.2 mm, size 2 × 3 cm) in 40% sodium hydroxide solution, and maintaining at 80 deg.C for 1 hr; then soaking the mixture in 6M HCl, and reacting for 2 hours at 90 ℃; taking out, washing with deionized water for several times, and soaking in anhydrous ethanol for use;
(2) Preparing a precursor solution containing antimony (Sb), tin (Sn) and tungsten (W);
weighing SnCl 4 ˙5H 2 O1.75 g was dissolved in 5ml of n-butanol solution as a tin-containing precursor solution, and SbCl was weighed 3 1.15g of antimony-containing precursor solution was dissolved in 5ml of n-butanol solution;
(3) Uniformly mixing 950 mu l of tin-containing precursor solution and 50 mu l of antimony-containing precursor solution, uniformly coating 200 mu l of the mixed solution on a titanium sheet, standing at room temperature for 1h, placing the titanium sheet as a substrate in a muffle furnace for roasting at 550 ℃ for 2h, controlling the heating rate to be 3 ℃/min, and naturally cooling to room temperature to obtain an antimony-doped tin dioxide/titanium sheet electrode;
(4) And (3) taking the electrode in the step (3) as a working electrode, a Pt sheet as a counter electrode, ag/AgCl as a reference electrode, 50ml of 100mg/L resorcinol as a solution to be degraded, 0.71g of electrolyte-containing anhydrous sodium sulfate, and the resorcinol degradation rate is 50% after 2 hours under the voltage of 3V.
Claims (9)
1. A method for manufacturing an electrode for the electrocatalytic degradation of resorcinol, comprising:
(1) Pretreating a titanium sheet with the thickness of 0.1 to 0.2 mm and the size of 2 multiplied by 3 cm;
(2) Preparing a precursor solution containing antimony (Sb), tin (Sn) and tungsten (W);
(3) Preparing antimony and tungsten co-doped tin dioxide SnO on the surface of a titanium sheet by using the titanium sheet as a substrate and adopting a thermal decomposition method 2 Catalyst to obtain Ti/Sb, W-SnO 2 An electrode;
(4) With Ti/Sb, W-SnO 2 A working electrode, a Pt sheet as a counter electrode, and nickel nitrate Ni (NO) 3 ) 2 The solution is electrolyte solution, and electrochemical deposition is carried out by adopting a constant current method to obtain the nickel-modified antimony and tungsten co-doped tin dioxide/titanium plate electrode.
2. The method for manufacturing an electrode for the electrocatalytic degradation of resorcinol according to claim 1, wherein the pre-treated titanium sheet comprises:
(1) Soaking the titanium sheet in a 40% sodium hydroxide solution, and keeping the temperature at 70-90 ℃ for 0.5-1h;
(2) Soaking the titanium sheet obtained in the step (1) in 6M HCl, and reacting at 80-90 ℃ for 1-2h;
(3) Washing the titanium sheet obtained in the step (2) with deionized water for several times, and finally soaking in absolute ethyl alcohol for later use.
3. The method for preparing an electrode for the electrocatalytic degradation of resorcinol according to claim 1, wherein said Ti/Sb, W-SnO is 2 The preparation of the electrode comprises:
(1) Respectively preparing SnCl with the concentration of 1mol/L 4 ˙5H 2 O n-butanol solution, 1mol/L SbCl 3 N-butanol solution, 1mol/L SnCl 4 ˙5H 2 O n-butanol solution, 1mol/L WCl 6 Ethanol solution;
(2) Taking the three solutions in the right amount (1) according to the doping ratio of antimony and tungsten, and carrying out ultrasonic treatment for 5 min to uniformly mix the three solutions;
(3) Uniformly coating 200 mu l of the mixed solution in the step (2) on a titanium sheet, and standing at room temperature for 1h;
(4) And (4) placing the titanium sheet obtained in the step (3) in a muffle furnace to be roasted for 2h at the temperature of 550 ℃, and controlling the heating rate to be 3 ℃/min. Finally naturally cooling to room temperature to obtain Ti/Sb, W-SnO 2 And an electrode.
4. The method for manufacturing the electrode for the electrocatalytic degradation of the resorcinol according to claim 1, wherein the doping proportion of antimony is 2% -5%, and the doping proportion of tungsten is 2% -5%. The concentration of the nickel nitrate is 0.1 to 0.5 mol/L, the constant current is-1 to-5 mA, and the electrodeposition time is 5 to 30min.
5. The method for producing an electrode for the electrocatalytic degradation of resorcinol according to any one of claims 1 to 4, which is produced by the steps of:
(1) Pre-treating a titanium sheet:
soaking a titanium sheet with the thickness of 0.1mm and the size of 2 multiplied by 3 cm in a 40 percent sodium hydroxide solution, and keeping the temperature at 80 ℃ for 1 hour; then soaking the mixture in 6M HCl, and reacting for 2 hours at 90 ℃; taking out, washing with deionized water for several times, and soaking in anhydrous ethanol for use;
(2) Preparing precursor solution containing antimony (Sb), tin (Sn) and tungsten (W)
Weighing SnCl 4 ˙5H 2 O1.75 g is dissolved in 5ml of n-butanol solution as a tin-containing precursor solution; weighing SbCl 3 1.15g of antimony-containing precursor solution was dissolved in 5ml of n-butanol solution; weighing WCl 6 1.98g of the precursor solution is dissolved in 5ml of ethanol solution to be used as a precursor solution containing tungsten;
(3) Taking a titanium sheet as a substrate, uniformly mixing 900 mu l of tin-containing precursor solution, 50 mu l of antimony-containing precursor solution and 50 mu l of tungsten-containing precursor solution, uniformly coating 200 mu l of the mixed solution on the titanium sheet obtained in the step (1), standing at room temperature for 1h, then roasting in a muffle furnace at 550 ℃ for 2h, controlling the heating rate to be 3 ℃/min, and finally naturally cooling to room temperature to obtain the tungsten and antimony co-doped tin dioxide/titanium sheet electrode to obtain Ti/Sb, W-SnO 2 An electrode;
(4) With Ti/Sb, W-SnO 2 As working electrode, pt sheet as counter electrode, with 50ml 0.1M nickel nitrate Ni (NO) 3 ) 2 The solution is electrolyte solution, electrochemical deposition is carried out by adopting a constant current method, the constant current is-1 mA, and the electrodeposition time is 0.5 h, so that the nickel-modified antimony and tungsten co-doped tin dioxide/titanium plate electrode is obtained.
6. The method for producing an electrode for the electrocatalytic degradation of resorcinol according to any one of claims 1 to 4, which is produced by the steps of:
(1) Pretreating a titanium sheet with the thickness of 0.1mm and the size of 2 multiplied by 3 cm:
soaking titanium sheet (thickness 0.1mm, size 2 × 3 cm) in 40% sodium hydroxide solution, and maintaining at 80 deg.C for 1 hr; then soaking the mixture in 6M HCl, and reacting for 2 hours at 90 ℃; taking out, washing with deionized water for several times, and soaking in anhydrous ethanol for use;
(2) Preparing a precursor solution containing antimony (Sb), tin (Sn) and tungsten (W):
weighing SnCl 4 ˙5H 2 O1.75 g was dissolved in 5ml of n-butanol solution as a tin-containing precursor solution, and SbCl was weighed 3 Dissolving 1.15g in 5ml n-butanol solution as antimony-containing precursor solution, and weighing WCl 6 1.98g of the precursor solution is dissolved in 5ml of ethanol solution to be used as a precursor solution containing tungsten;
(3) Uniformly mixing 925 mu l of tin-containing precursor solution, 25 mu l of antimony-containing precursor solution and 50 mu l of tungsten-containing precursor solution, uniformly coating 200 mu l of the mixed solution on a titanium sheet, placing the titanium sheet at room temperature for 1h, placing the titanium sheet as a substrate in a muffle furnace for roasting at 550 ℃ for 2h, controlling the heating rate to be 3 ℃/min, and naturally cooling to room temperature to obtain the antimony and tungsten co-doped tin dioxide SnO 2 Catalyst to obtain Ti/Sb, W-SnO 2 An electrode;
(4) With Ti/Sb, W-SnO 2 As working electrode, pt sheet as counter electrode, with 50ml 0.1M nickel nitrate Ni (NO) 3 ) 2 And performing electrochemical deposition by adopting a constant current method with constant current of-1 mA and electro-deposition time of 0.5 h to obtain the nickel-modified antimony and tungsten co-doped tin dioxide/titanium plate electrode.
7. The method for producing an electrode for the electrocatalytic degradation of resorcinol according to any one of claims 1 to 4, which is produced by the steps of:
(1) Pretreating a titanium sheet with the thickness of 0.1mm and the size of 2 multiplied by 3 cm:
soaking titanium sheet (thickness 0.1mm, size 2 × 3 cm) in 40% sodium hydroxide solution, and maintaining at 80 deg.C for 1 hr; then soaking the mixture in 6M HCl, and reacting for 2 hours at 90 ℃; taking out, washing with deionized water for several times, and soaking in anhydrous ethanol for use;
(2) Preparing a precursor solution containing antimony (Sb), tin (Sn) and tungsten (W):
weighing SnCl 4 ˙5H 2 O1.75 g was dissolved in 5ml of n-butanol solution as a tin-containing precursor solution, and SbCl was weighed 3 1.15g of antimony-containing precursor solution was dissolved in 5ml of n-butanol solution, and WCl was weighed 6 1.98g of the precursor solution is dissolved in 5ml of ethanol solution to be used as a precursor solution containing tungsten;
(3) Uniformly mixing 950 mul of tin-containing precursor solution, 25 mul of antimony-containing precursor solution and 25 mul of tungsten-containing precursor solution, uniformly coating 200 mul of the mixed solution on a titanium sheet, taking the titanium sheet as a substrate, standing at room temperature for 1h, then placing the titanium sheet in a muffle furnace for roasting at 550 ℃ for 2h, controlling the heating rate to be 3 ℃/min, and preparing antimony and tungsten co-doped tin dioxide SnO on the surface of the titanium sheet by adopting a thermal decomposition method 2 Catalyst to obtain Ti/Sb, W-SnO 2 An electrode;
(4) With Ti/Sb, W-SnO 2 As working electrode, pt sheet as counter electrode, with 50ml 0.1M nickel nitrate Ni (NO) 3 ) 2 And performing electrochemical deposition by adopting a constant current method with constant current of-1 mA and electro-deposition time of 0.5 h to obtain the nickel-modified antimony and tungsten co-doped tin dioxide/titanium plate electrode.
8. An electrode for the electrocatalytic degradation of resorcinol, which is characterized by being produced by the method of any one of claims 1 to 7, and specifically comprises the following steps: a titanium sheet substrate; the titanium sheet substrate is covered with an antimony-tungsten co-doped tin dioxide catalyst; and a nickel hydroxide or nickel oxide protective layer is deposited on the surface of the antimony-tungsten co-doped stannic oxide catalyst.
9. The nickel-modified Ti/Sb, W-SnO of claim 8 2 The application of the electrode for electrocatalytic degradation of resorcinol at normal temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210969254.9A CN115259295A (en) | 2022-08-12 | 2022-08-12 | Electrode manufacturing method for degrading resorcinol by electrocatalysis, product and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210969254.9A CN115259295A (en) | 2022-08-12 | 2022-08-12 | Electrode manufacturing method for degrading resorcinol by electrocatalysis, product and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115259295A true CN115259295A (en) | 2022-11-01 |
Family
ID=83750283
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210969254.9A Pending CN115259295A (en) | 2022-08-12 | 2022-08-12 | Electrode manufacturing method for degrading resorcinol by electrocatalysis, product and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115259295A (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1373712A (en) * | 1971-03-20 | 1974-11-13 | Conradty Fa C | Electrode for electrochemical processes |
| US5470673A (en) * | 1991-03-01 | 1995-11-28 | University Of Essex | Electrochromic and electrocatalytic material |
| US20040031692A1 (en) * | 1999-06-28 | 2004-02-19 | Kenneth Hardee | Coatings for the inhibition of undesirable oxidation in an electrochemical cell |
| CN101580270A (en) * | 2009-06-26 | 2009-11-18 | 上海大学 | Method for preparing nano-doped tin oxide sol |
| CN103449508A (en) * | 2013-07-31 | 2013-12-18 | 深圳大学 | Tungsten doped tin dioxide nano powder and preparation method thereof |
| JP2015176794A (en) * | 2014-03-17 | 2015-10-05 | 国立大学法人山梨大学 | Carrier for electrode catalyst, and electrode catalyst and fuel battery that use the same |
| CN105540650A (en) * | 2016-02-25 | 2016-05-04 | 攀枝花学院 | Tungsten-doped stannic oxide sol nanocrystalline and preparing method thereof |
| CN114105258A (en) * | 2021-11-17 | 2022-03-01 | 上海纳米技术及应用国家工程研究中心有限公司 | Manufacturing method of electrode for electrocatalytic degradation of pyridine, product and application thereof |
| CN114737215A (en) * | 2022-03-31 | 2022-07-12 | 福建工程学院 | Preparation method of nickel-tungsten composite electrode and application of nickel-tungsten composite electrode in electrocatalytic oxidation |
-
2022
- 2022-08-12 CN CN202210969254.9A patent/CN115259295A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1373712A (en) * | 1971-03-20 | 1974-11-13 | Conradty Fa C | Electrode for electrochemical processes |
| US5470673A (en) * | 1991-03-01 | 1995-11-28 | University Of Essex | Electrochromic and electrocatalytic material |
| US20040031692A1 (en) * | 1999-06-28 | 2004-02-19 | Kenneth Hardee | Coatings for the inhibition of undesirable oxidation in an electrochemical cell |
| TW200417634A (en) * | 2002-10-18 | 2004-09-16 | Eltech Systems Corp | Coatings for the inhibition of undesirable oxidation in an electrochemical cell |
| CN101580270A (en) * | 2009-06-26 | 2009-11-18 | 上海大学 | Method for preparing nano-doped tin oxide sol |
| CN103449508A (en) * | 2013-07-31 | 2013-12-18 | 深圳大学 | Tungsten doped tin dioxide nano powder and preparation method thereof |
| JP2015176794A (en) * | 2014-03-17 | 2015-10-05 | 国立大学法人山梨大学 | Carrier for electrode catalyst, and electrode catalyst and fuel battery that use the same |
| CN105540650A (en) * | 2016-02-25 | 2016-05-04 | 攀枝花学院 | Tungsten-doped stannic oxide sol nanocrystalline and preparing method thereof |
| CN114105258A (en) * | 2021-11-17 | 2022-03-01 | 上海纳米技术及应用国家工程研究中心有限公司 | Manufacturing method of electrode for electrocatalytic degradation of pyridine, product and application thereof |
| CN114737215A (en) * | 2022-03-31 | 2022-07-12 | 福建工程学院 | Preparation method of nickel-tungsten composite electrode and application of nickel-tungsten composite electrode in electrocatalytic oxidation |
Non-Patent Citations (2)
| Title |
|---|
| 方度: "《氯碱工艺学》", 化学工业出版社, pages: 69 * |
| 曾郴林: "《电化学法废水处理技术及其应用》", 31 January 2022, 中国环境出版集团, pages: 70 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101525755B (en) | Cathode for hydrogen generation | |
| Lim et al. | Influence of the Sb content in Ti/SnO2-Sb electrodes on the electrocatalytic behaviour for the degradation of organic matter | |
| JP5553605B2 (en) | Cathode for electrolytic process | |
| CN100412233C (en) | Technological method for treating carbolic acid waste water by electrochemical oxidation | |
| JPS6231075B2 (en) | ||
| JP4673628B2 (en) | Cathode for hydrogen generation | |
| da Silva et al. | Influence of heating rate on the physical and electrochemical properties of mixed metal oxides anodes synthesized by thermal decomposition method applying an ionic liquid | |
| CN110639525A (en) | Nickel oxide nanoflower/foamed nickel and electrodeposition preparation and application thereof | |
| JP2014517158A (en) | Oxygen generating anode | |
| CN113526622A (en) | Foamed nickel loaded porous carbon coated nickel tin-iron nickel alloy electrode material and preparation method and application thereof | |
| CN114105258A (en) | Manufacturing method of electrode for electrocatalytic degradation of pyridine, product and application thereof | |
| CN111530474A (en) | Noble metal monoatomic regulation spinel array catalyst and preparation method and application thereof | |
| KR101110091B1 (en) | Electrode for electrochemical processes and method for producing the same | |
| CN115259295A (en) | Electrode manufacturing method for degrading resorcinol by electrocatalysis, product and application | |
| CN110302772B (en) | Supported photocatalytic material and preparation method thereof | |
| KR20190067354A (en) | method for manufacturing graphene complex electrolysis electrodes for wastewater processing and sterilization | |
| CN109824126B (en) | Tin oxide anode electrode with high oxygen evolution potential and preparation method | |
| CN108046380B (en) | Titanium-based Sn-Sb-Ce oxide electrode and preparation method and application thereof | |
| CN109553160B (en) | Preparation method and application of in-situ synthesized spherical tin dioxide platinum-loaded electrocatalyst | |
| CN102505127A (en) | Preparation method for noble metal modified titanium anode materials | |
| KR20170093039A (en) | Double-layer oxidizing electrode with metal ion concentration gradient and method for fabricating the same | |
| CN115807241A (en) | Ultrathin iridium-based nanosheet catalyst, and preparation method and application thereof | |
| Okunaka et al. | Controlling the selectivity of solar O2/HClO production from seawater by simple surface modification of visible-light responsible photoelectrodes | |
| KR102577725B1 (en) | A hydrogen evolution reaction catalytic electrode, its manufacturing method, and the hydrogen production method by water electrolysis using it | |
| CN114044560A (en) | Manufacturing method of electrode for degrading nitrobenzene through electrocatalysis, product and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |