CN112110523A

CN112110523A - Preparation method and application of titanium-based copper oxide doped tin antimony oxide electrode

Info

Publication number: CN112110523A
Application number: CN202011049229.6A
Authority: CN
Inventors: 宋启军; 王婵; 孙国巍; 李德慧
Original assignee: Jiangnan University
Current assignee: Jiangnan University
Priority date: 2020-09-29
Filing date: 2020-09-29
Publication date: 2020-12-22
Anticipated expiration: 2040-09-29
Also published as: CN112110523B

Abstract

The invention discloses a preparation method and application of a titanium-based copper oxide doped tin antimony oxide electrode, and belongs to the field of electrode material preparation. The method for preparing the copper oxide doped tin-antimony oxide electrode comprises the following steps: carrying out pretreatment, ultrasonic copper activation, chemical deposition of tin and antimony and calcination on a titanium substrate to obtain a copper oxide doped tin-antimony oxide electrode; wherein, the A solution adopted for chemically depositing the tin and the antimony contains thiourea, acetic acid, sodium dihydrogen phosphate, OP-10 and polyethylene glycol; sulfuric acid, citric acid, tin salt and SbCl in the solution B₃The mass-to-volume ratio of (a) is 90 uL: 1.5 g: 0.575 g-3.45 g: 12-48 mg; the calcination is carried out at 400-650 ℃ for 4-8 h. The copper oxide doped tin antimony oxide electrode prepared by the invention has high oxygen evolution potential reaching 2.13V (vs. SHE), is suitable for complete degradation of refractory wastewater, and can realize almost complete degradation of 20mg/L dye within 100 min.

Description

Preparation method and application of titanium-based copper oxide doped tin antimony oxide electrode

Technical Field

The invention relates to a preparation method and application of a titanium-based copper oxide doped tin antimony oxide electrode, belonging to the field of electrode material preparation.

Background

Along with the developing national industryThe industrialization has the advantages of extremely accelerating development, great discharge of three industrial wastes and gradually attaching attention to the environmental protection problem by human beings, the treatment of industrial wastewater is a global problem to be solved urgently, and the current treatment means of industrial wastewater can be divided into a chemical method, a physical method, a photocatalytic method, an electrocatalytic method and a photoelectrocatalytic method. The electrocatalysis method has the advantages of simple equipment, simple operation, no secondary pollution, complete degradation and the like. Is considered to be one of the important ways for industrially solving the sewage problem. However, the existing electrocatalytic degradation technology still has a series of problems, such as low catalytic efficiency, short service life, incapability of realizing industrialized preparation and the like. The number of anodes used for electrocatalytic oxidation is approximately 3, one is a carbon anode such as carbon felt, graphite and boron-doped diamond; an electrode of titanium-based metal oxide such as Ti/SnO₂-Sb，Ti/PbO₂，Ti/RuO₂-Ir，Ti/IrO₂-Ta, etc. electrodes; the other is an anode of the Fe plate which is self-sacrifice and participates in the Fenton reaction to generate hydroxyl radicals. The boron-doped diamond electrode has high preparation requirement due to expensive raw materials, can only stay in a laboratory research stage at present, and is not easy to be applied industrially. The titanium-based tin antimony oxide electrode has the characteristics of low raw material price, high oxygen evolution potential, excellent catalytic performance and the like, and is very likely to be applied to future environmental purification.

The existing preparation method of the metal oxide electrode comprises the following steps: chemical thermal decomposition, spray pyrolysis, sol-gel process, electrodeposition, and also physical processes in recent years in combination with preparation methods such as: CVD, PVD, magnetron sputtering, and the like. The surface of the electrode has cracks with different degrees in the traditional method, and the service life is seriously influenced. The chemical deposition has the advantages of no dead angle, low energy consumption, simple preparation of the precursor and the like. However, since the titanium substrate is easily oxidized to form a thin oxide film, it is difficult to directly chemically deposit active materials on the surface of the titanium substrate.

Disclosure of Invention

In order to solve at least one problem, the invention provides a method for preparing an ultrathin, compact, highly dispersed and efficient tin-antimony oxide electrode with copper oxide doping on the surface by using a chemical deposition and calcination mode, so that the compactness of a film and the degradation efficiency of the electrode are improved. After proper pretreatment, ultrasonic-assisted hydrofluoric acid etching and chemical displacement copper plating are carried out in the same system; then soaking the activated anode in a precursor solution of chemical tin-antimony plating for chemical replacement to obtain a tin-antimony simple substance layer, thereby realizing the chemical deposition of double metals together; calcining at high temperature in air atmosphere, and infiltrating the surface tin-antimony part into the copper activation layer to obtain the copper-containing titanium-based tin-antimony oxide coating. The ultrathin oxide coating has good improvement on the conductivity of the electrode, and the surface doping of the copper oxide greatly improves the oxygen precipitation potential on the surface of the anode, so that the generation efficiency of active oxygen is improved, and the electrocatalytic oxidation degradation efficiency is enhanced.

A first object of the present invention is to provide a method for preparing a copper oxide doped tin antimony oxide electrode, comprising the steps of:

(1) pretreatment: cleaning a titanium substrate in an alkali solution, and etching in an acid solution to obtain a pretreated titanium substrate;

(2) ultrasonic copper activation: carrying out ultrasonic treatment on the pretreated titanium substrate in a mixed solution of hydrofluoric acid, copper salt and CTAB to obtain an activated titanium substrate;

(3) chemical deposition of tin and antimony: preparing solution A and solution B, wherein the solution A contains thiourea, acetic acid, sodium dihydrogen phosphate, OP-10 and polyethylene glycol; the solution B contains sulfuric acid, citric acid, tin salt and SbCl₃(ii) a Then putting the activated titanium substrate into the mixed solution of A, B liquid for chemical deposition; obtaining a titanium substrate after chemical tinning and antimony simple substance;

(4) and (3) calcining: and calcining the titanium substrate after chemical tinning and antimony simple substance plating to obtain the copper oxide doped tin-antimony oxide electrode.

In one embodiment of the invention, the alkali solution in the step (1) is one or two of a sodium hydroxide solution and a sodium carbonate solution, wherein the concentration of sodium hydroxide is 3-10 wt%, and the concentration of sodium carbonate is 1-5 wt%.

In one embodiment of the invention, the ultrasonic cleaning in the step (1) is 53kHz and 250W ultrasonic for 20-100 min.

In one embodiment of the invention, the acid solution in the step (1) is oxalic acid solution, and the etching is performed at 60-100 ℃ for 4-7 h.

In one embodiment of the present invention, the concentration of hydrofluoric acid in the mixed solution of step (2) is 1 to 2 vol%, the concentration of copper salt is 1.0 to 3.0 wt%, and the concentration of CTAB is 10 to 30 mg/L.

In one embodiment of the present invention, the copper salt in step (2) is CuSO₄·5H₂O、CuCl₂、Cu(NO₃)₂One or more of them.

In one embodiment of the present invention, the ultrasonic treatment in step (2) is ultrasonic treatment at 53kHz and 250W for 3-6 min, and more preferably 3 min.

In one embodiment of the present invention, the temperature for activation in step (2) is 25 to 45 ℃.

In one embodiment of the invention, the mass-to-volume ratio of thiourea, acetic acid, sodium dihydrogen phosphate, OP-10 and polyethylene glycol in the solution A in step (3) is 81.25 g: 12.5 mL: 15: 0.75 mL: 3.125 g.

In one embodiment of the present invention, the solution B of step (3) contains sulfuric acid, citric acid, tin salt, and SbCl₃The mass-to-volume ratio of (a) is 90 uL: 1.5 g: 0.575 g-3.45 g: 12-48 mg; more preferably 90 uL: 1.5 g: 1.15 g: 24 mg.

In one embodiment of the invention, the volume ratio of the liquid A to the liquid B in the step (3) is (3-10): 1, more preferably 4 to 8: 1, more preferably 4: 1.

in one embodiment of the present invention, the time of the chemical deposition in the step (3) is 100 to 400 seconds, and the temperature is 500 ℃.

In one embodiment of the present invention, the tin salt in step (3) is one or both of stannous sulfate and stannous chloride.

In one embodiment of the present invention, the calcination in step (4) is 400 to 650 ℃ for 4 to 8 hours, and more preferably 500 ℃ for 6 hours.

In one embodiment of the present invention, the calcination in step (4) is calcination in an air atmosphere.

The second purpose of the invention is to obtain the copper oxide doped tin antimony oxide electrode prepared by the method.

The third purpose of the invention is to apply the copper oxide doped tin antimony oxide electrode in degrading phenolic organic matters or dye substances in organic wastewater.

In one embodiment of the present invention, the phenolic organic compound is 4-nitrophenol.

In one embodiment of the invention, the dye substance is one or two of methylene blue and rhodamine B.

The fourth purpose of the invention is to provide a titanium-based ultrasonic copper plating method, which comprises the following steps:

(2) ultrasonic copper plating: and (3) carrying out ultrasonic treatment on the pretreated titanium substrate in a mixed solution of hydrofluoric acid, copper salt and CTAB to obtain the titanium substrate after ultrasonic copper plating.

A fifth object of the present invention is to provide a method for preparing a tin single layer, comprising the steps of:

(3) chemical deposition of tin and antimony: preparing solution A and solution B, wherein the solution A contains thiourea, acetic acid, sodium dihydrogen phosphate, OP-10 and polyethylene glycol; the solution B contains sulfuric acid, citric acid and tin salt; then putting the activated titanium substrate into the mixed solution of A, B liquid for chemical deposition; obtaining the titanium substrate after chemically plating the tin simple substance.

In one embodiment of the present invention, the mass volume ratio of the sulfuric acid, the citric acid and the tin salt in the solution B in step (3) is 90 uL: 1.5 g: 0.575 g-3.45 g; more preferably 90 uL: 1.5 g: 1.15 g.

a fifth object of the present invention is to provide a method for preparing an antimony single layer, comprising the steps of:

(3) chemical deposition of tin and antimony: preparing solution A and solution B, wherein the solution A contains thiourea, acetic acid, sodium dihydrogen phosphate, OP-10 and polyethylene glycol; the solution B contains sulfuric acid, citric acid and SbCl₃(ii) a Then putting the activated titanium substrate into the mixed solution of A, B liquid for chemical deposition; obtaining the titanium substrate after chemical antimony plating.

In one embodiment of the present invention, the solution in step (3) B contains sulfuric acid, citric acid, and SbCl₃The mass-to-volume ratio of (a) is 90 uL: 1.5 g: 12-48 mg; more preferably 90 uL: 1.5 g: 24 mg.

the invention has the beneficial effects that:

(1) the copper oxide doped tin antimony oxide electrode prepared by the invention has the advantages that the high oxygen evolution potential reaches 2.13V (vs. SHE), the electrode preparation operation is simple and rapid, tin and antimony deposition is firm, the mechanical property is good, the chemical plating process can be completed within 10min, the copper oxide doped tin antimony oxide electrode is suitable for complete degradation of refractory wastewater, and the almost complete degradation of 20mg/L dye can be realized within 100 min.

(2) The invention provides a preparation method of a copper oxide doped tin antimony oxide electrode, which is rapid, easy to industrially prepare and high in catalytic activity. The chemical plating realizes a tighter dead-angle-free plating layer on the titanium-based surface, and the tin-antimony oxide and the copper oxide deposited on the titanium-based surface are densely stacked by the microspheres with the nanometer particle size, so that the specific surface area of the electrode is greatly enhanced, and the catalytic degradation efficiency is improved. Meanwhile, the usage amount of hydrofluoric acid and tin-antimony solution is greatly reduced, and the preparation cost is saved.

Drawings

FIG. 1 is a cold field Scanning Electron Microscope (SEM) photograph of the electrolessly deposited tin antimony of example 1.

FIG. 2 is a cold field Scanning Electron Microscope (SEM) photograph of example 1 after calcination of chemically deposited tin antimony.

FIG. 3 is a UV spectrum of the methylene blue degradation process of example 1.

FIG. 4 is a photograph of the discoloration during the degradation of methylene blue of example 1.

FIG. 5 is a UV spectrum of the degradation process of 4-nitrophenol of example 1.

Fig. 6 is a surface oxygen evolution potential (LSV) curve of the electrode of example 1.

Detailed Description

The following description of the preferred embodiments of the present invention is provided for the purpose of better illustrating the invention and is not intended to limit the invention thereto.

The test method comprises the following steps:

cold field scanning electron microscope: (S-4800, Japan)

An electrochemical workstation: (CHI660D, Shanghai)

Ultraviolet spectrophotometer: (UV-2700)

Testing of degradation rate: percent degradation is (1-A)_t/A₀)×100％

Wherein A is_tFor the UV absorbance value of the degradation product during degradation, A₀The UV absorbance of the initial solution.

Example 1

A method of making a copper oxide doped tin antimony oxide electrode comprising the steps of:

(1) pretreatment: preparing NaOH (4 wt%) and Na₂CO₃(2 wt%) 100mL of solution, a batch of 3cm by 0.5cm titanium substrates was immersed in the solution and sonicated at 53kHz, 250W for 30 min; washing the degreased titanium substrate with clear water, soaking the degreased titanium substrate into an oxalic acid (15 wt%) solution, controlling the temperature of the solution to 98 ℃, etching the solution for 5 hours, taking out the solution, and cleaning the solution to obtain a pretreated titanium substrate;

(2) ultrasonic copper plating: prepared hydrofluoric acid (1.5 vol%), CuSO₄·5H₂Putting a solution of O (1.5 wt%) and CTAB (trace 15mg/L) into an ultrasonic water bath kettle, and controlling the temperature of the solution to be 30 +/-2 ℃; selecting ultrasonic frequency power of 53kHz and 250W respectively, then starting an ultrasonic machine, immersing the pretreated titanium substrate in the ultrasonic frequency power for 3min, taking out the titanium substrate, and immediately cleaning the titanium substrate with water; obtaining a titanium substrate after copper plating;

(3) chemical tin and antimony plating: preparing chemical plating solution A, B; wherein the A liquid is 40 mL: 3.25g of thiourea, 500 mu L of acetic acid, 0.6g of sodium dihydrogen phosphate, OP-1030 mu L of sodium dihydrogen phosphate and 0.125g of polyethylene glycol; 10mL of solution B, 90 mu L of sulfuric acid, 1.5g of citric acid and SnCl₂1.15g、SbCl₃24 mg; mixing the A, B solution, putting the titanium substrate plated with copper into the solution, soaking for 135s, taking out and cleaning to obtain the titanium substrate plated with the chemical tin and antimony simple substance; the morphology is shown in FIG. 1. (note that the use effect of the electrode plate is influenced by the fact that the stay time in the middle of the continuous process is too long in the first three steps of operation.)

(4) High-temperature calcination: drying the titanium plate chemically plated with the tin antimony simple substance by nitrogen, and then putting the titanium plate into a tubular furnace to calcine in the air atmosphere; and (3) setting the temperature rise rate to be 2 ℃/min and keeping the temperature for 6 hours when the temperature reaches 500 ℃, so as to obtain the copper oxide doped tin antimony oxide electrode, wherein the appearance is shown in figure 2.

And (3) degradation process: and taking a harmful substance (methylene blue, rhodamine B and p-nitrophenol) solution with the mass concentration of 20mg/L as an organic matter solution to be degraded, and taking 0.25mol/L sodium sulfate as an electrolyte. And (3) taking 200mL of solution to be degraded, taking a prepared copper oxide doped tin antimony oxide electrode as an anode, taking two stainless steel plates as a cathode, and controlling the current to be 0.1A for degradation for 100min, wherein the interval between the three plates is 2 cm.

FIG. 3 is a UV spectrum of the degradation process of methylene blue. FIG. 4 is a photograph of the discoloration during the degradation of methylene blue of example 1. As can be seen from fig. 3 and 4: as the degradation time increased, the methylene blue was substantially completely degraded in 100 minutes. The above degradation process was repeated 10 times, and the degradation effect of methylene blue is shown in Table 1.

TABLE 1 degradation rate of cyclic degradation of methylene blue

Number of cycles	Degradation Rate (%)
		1	97.2
2	96.0
		3	91.5
4	90.0
		5	92.0
6	91.5
		7	93.0
8	88.0
		9	83.2
10	85.0

The degradation effect of rhodamine B is shown in Table 2.

TABLE 2 degradation Effect of rhodamine B

Degradation time (min)	Balance (%)	Degradation Rate (%)
			0	1	0
20	0.65752	34.2
			40	0.4929	50.7
60	0.28477	71.5
			80	0.15421	84.6
100	0.05582	94.4

The degradation effect of 4-nitrophenol is shown in Table 3; FIG. 5 is a UV spectrum of the degradation process of 4-nitrophenol of example 1. As can be seen from fig. 5: with the increase of the degradation time, the ultraviolet peak of the 4-nitrophenol disappears at 140 minutes, which shows that the 4-nitrophenol is almost completely degraded at 400nm, but small molecular organic pollutants obtained after ring opening exist, and with the continuous increase of the degradation time to 240 minutes, the small molecular ultraviolet peak at 320nm is basically not existed, which shows that the 4-nitrophenol is completely mineralized.

TABLE 34 degradation Effect of nitrophenols

Degradation time (min)	Balance (%)	Degradation Rate (%)
			0	1	0
20	0.59478	40.5
			40	0.4013	59.9
60	0.2787	72.1
			80	0.20217	79.8
100	0.1287	87.1
			120	0.068	93.2

Electrode surface oxygen evolution potential (LSV) curve test: tin oxide electrode and antimony oxide electrode (purchased from Baojie Longsheng nonferrous metals Co., Ltd.) and the electrode prepared in example 1 were taken as working electrodes, saturated calomel electrode was taken as a reference electrode, platinum wire was taken as a counter electrode, the scanning speed was set to 0.01V/s, the scanning voltage was set to 0 to 3V, 50 ml of 0.5M sulfuric acid solution in electrolytic liquid level was selected, the oxygen evolution potential was regarded as the potential value of the intersection point of the tangent line of the current density rising section curve and the X axis, see FIG. 6, and the high oxygen evolution potential of the electrode in example 1 reached 2.13V (vs. SHE).

Example 2

(1) pretreatment: preparing 100mL of NaOH (10 wt%) solution, immersing a batch of 3cm by 0.5cm titanium substrates in the solution, and carrying out ultrasonic treatment at 53kHz and 250W for 1 hour; washing the degreased titanium substrate with clear water, soaking the degreased titanium substrate into an oxalic acid (15 wt%) solution, controlling the temperature of the solution to 98 ℃, etching the solution for 3 hours, and taking out the solution to clean the solution for later use; obtaining a pretreated titanium substrate;

(2) ultrasonic copper plating: prepared hydrofluoric acid (1.0 vol%), CuCl₂(2.0 wt%) and CTAB (trace amount of 20mg/L) solution are put into an ultrasonic water bath kettle, the temperature of the solution is controlled to be 40 ℃ for ultrasonic treatment, ultrasonic frequency power is selected to be 53kHz and 250W respectively, then an ultrasonic machine is started, the pretreated titanium substrate is immersed in the ultrasonic frequency power for 3min and then taken out, and the titanium substrate is cleaned; obtaining a titanium substrate after copper plating;

(3) chemical tin and antimony plating: preparing chemical plating solution A, B; 40mL of solution A: 3.25g of thiourea, 500 mu L of acetic acid, 0.6g of sodium hypophosphite, OP-1030 mu L of sodium hypophosphite and 0.125g of polyethylene glycol; 10mL of solution B, 90 mu L of sulfuric acid, 1.5g of citric acid and SnSO₄2g、SbCl₃30 mg; mixing the A, B solution, putting the mixture into a copper-plated titanium plate, soaking the titanium plate in the solution for 240s, taking out and cleaning the titanium plate; obtaining a titanium substrate after chemical tin and antimony plating;

(4) high-temperature calcination: and (3) drying the titanium substrate chemically plated with the tin and antimony simple substance by nitrogen, then placing the titanium substrate into a tubular furnace to calcine in the air atmosphere, and keeping the temperature for 4 hours when the temperature rise rate is set to be 5 ℃/min and the temperature reaches 600 ℃, so as to obtain the copper oxide doped tin-antimony oxide electrode.

And (3) degradation process: 20mg/L of rhodamine B is taken as an organic matter to be degraded, and 0.25mol/L of sodium sulfate is taken as an electrolyte. And (3) taking 200mL of solution to be degraded, taking the prepared copper oxide doped tin antimony oxide electrode as an anode, taking two stainless steel plates as a cathode, and degrading for 100min at the interval of 2cm between the three polar plates under the control of current of 0.1A, wherein the solution becomes colorless.

Example 3

(1) pretreatment of: preparation of Na₂CO₃(4 wt%) of the solution 100mL, a batch of 3cm by 0.5cm titanium substrates was immersed in the solution and sonicated for 60 min; washing the degreased titanium substrate with clear water, soaking the degreased titanium substrate into an oxalic acid (10 wt%) solution, controlling the temperature of the solution to 98 ℃, etching the solution for 6 hours, taking out the solution, and cleaning the solution for later use to obtain a pretreated titanium substrate;

(2) ultrasonic copper plating: prepared hydrofluoric acid (1.5 vol%), Cu (NO)₃)₂(1.5 wt%) and CTAB (15mg/L) are put into an ultrasonic water bath kettle, the temperature of the solution is controlled to be 30 +/-2 ℃, ultrasonic frequency power is selected to be 53kHz and 250W respectively, then an ultrasonic machine is started, the pretreated titanium substrate is immersed in the ultrasonic solution for 3min and then taken out, and water is immediately cleaned to obtain a copper-plated titanium substrate;

(3) chemical tin and antimony plating: preparing chemical plating solution A, B; 40mL of solution A: 3.25g of thiourea, 500 mu L of acetic acid, 0.6g of sodium dihydrogen phosphate, OP-1030 mu L of sodium dihydrogen phosphate and 0.125g of polyethylene glycol; 10mL of solution B: sulfuric acid 200 mu L, citric acid 1.5g and SnSO₄1.15g、SbCl₃48 mg; mixing the A, B solution, putting the mixture into a copper-plated titanium substrate, soaking the titanium substrate in the solution for 135s, taking out the titanium substrate, and cleaning the titanium substrate to obtain the titanium substrate after chemical tin and antimony plating;

(4) high-temperature calcination: drying the titanium plate chemically plated with the tin antimony simple substance by nitrogen, and then putting the titanium plate into a tubular furnace to calcine in the air atmosphere; and keeping the temperature for 6 hours when the temperature rise rate is set to be 2 ℃/min and the temperature reaches 500 ℃, thus obtaining the copper oxide doped tin antimony oxide electrode.

And (3) degradation process: 20mg/L of p-nitrophenol is taken as an organic matter to be degraded, and 0.25mol/L of sodium chloride is taken as an electrolyte; and (3) taking 200mL of solution to be degraded, taking a prepared copper oxide doped tin antimony oxide electrode as an anode, taking two stainless steel plates as a cathode, and controlling the current to be 0.1A for degradation for 100min at an interval of 2cm between the three electrode plates to almost completely degrade.

Example 4

The calcining temperature of the step (4) in the example 1 is adjusted to 400, 500 and 650 ℃, and other preparation parameters are kept consistent with those of the example 1, so that the copper oxide doped tin antimony oxide electrode is obtained.

The obtained copper oxide doped tin antimony oxide electrode is subjected to a methylene blue degradation experiment, and the test data are shown in table 4.

TABLE 4 degradation ratio (%) -of copper oxide doped tin antimony oxide electrode obtained at different calcination temperatures

Degradation time min	400℃	500 deg.C (example 1)	650℃
				0	0	0	0
20	19.6	40.4	27
				40	39.2	64.0	52.7
60	52.9	81.8	69.2
				80	64.8	93.0	82.5
100	68.8	97.2	84.8

Example 5

SbCl obtained in step (3) of example 1 was adjusted₃The amounts of the copper oxide doped tin antimony oxide electrode were 0, 12, 24, 48 and 60mg, and the others were kept the same as in example 1.

The obtained copper oxide doped tin antimony oxide electrode is subjected to a methylene blue degradation experiment, and the test data are shown in table 5.

TABLE 5 different SbCl₃Degradation ratio (%)% of copper oxide-doped tin antimony oxide electrode obtained in the amount of

Time of degradation	0	12mg	24mg (example 1)	48mg	60mg
							0	0	0	0	0	0
20	26.2	34.2	40.4	29.3	23.0
						40	58.8	66.6	64.0	65.9	45.2
60	69.9	81.1	81.8	82.0	61.2
						80	75	88.2	93.0	92.6	71.6
100	79.4	89.7	97.2	93.8	75.5

Example 6

The mixing volume ratio of the A, B solution obtained in step (3) of example 1 was adjusted as shown in table 6, and other production parameters were kept the same as those in example 1, thereby obtaining a copper oxide-doped tin antimony oxide electrode.

The obtained copper oxide doped tin antimony oxide electrode is subjected to a degradation experiment, and the test data are shown in table 6.

TABLE 6 degradation ratio (%) -of copper oxide-doped tin antimony oxide electrode obtained at different A, B liquid ratios

Example 7

Adjustment of SnCl in step (3) in example 1₂The amounts of copper oxide doped tin antimony oxide electrodes were as in table 7, otherwise consistent with example 1.

The obtained copper oxide doped tin antimony oxide electrode was subjected to methylene blue degradation experiments, and the test data are shown in table 7.

TABLE 7 different SnCl₂The degradation rate of the copper oxide doped tin antimony oxide electrode obtained by the dosage

SnCl₂Amount of (g)	Degradation Rate (%)
		1.15 (example 1)	97.2
0.575	95.0
		2.30.	92.0
3.45	90.0
		0.4	Unstable electrode and failure to prepare

Example 8

The time for ultrasonic copper plating in step (2) of example 1 was adjusted as shown in table 8, and the others were kept the same as in example 1, to obtain a copper oxide-doped tin antimony oxide electrode.

Copper oxide doped tin antimony oxide electrodes were observed and the results are shown in table 8.

TABLE 8 copper plating results for copper oxide doped tin antimony oxide electrodes obtained at different ultrasonic copper plating times

Copper plating time	Results of copper plating
		60s	The titanium surface is successfully plated in a small area
120s	Has a certain copper plating defect
		180s	Almost completely full of
240s	Excessive thickness of the plating layer, insufficient surface bonding, surface copperIs easy to fall off

Comparative example 1

The calcination in step (4) of example 1 was omitted to obtain an electrode.

The obtained electrode is subjected to methylene blue degradation experiments, and the electrode is found to be directly dissolved away because the methylene blue degradation cannot be realized at all.

Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.

Claims

1. A method for preparing a copper oxide doped tin antimony oxide electrode is characterized by comprising the following steps:

(3) chemical deposition of tin and antimony: preparing solution A and solution B, wherein the solution A contains thiourea, acetic acid, sodium dihydrogen phosphate, OP-10 and polyethylene glycol; the solution B contains sulfuric acid, citric acid, tin salt and SbCl₃(ii) a Then putting the activated titanium substrate into a mixed solution of A, B liquid for chemical deposition to obtain the titanium substrate after chemical tin and antimony elementary substances plating;

2. The method according to claim 1, wherein the mixed solution of step (2) has a hydrofluoric acid concentration of 1 to 2 vol%, a copper salt concentration of 1.0 to 3.0 wt%, and a CTAB concentration of 10 to 30 mg/L.

3. The method according to claim 1 or 2, wherein the ultrasonic treatment in the step (2) is ultrasonic treatment at 53kHz and 250W for 3-6 min.

4. The method according to any one of claims 1 to 3, wherein the solution B in step (3) contains sulfuric acid, citric acid, tin salt, SbCl₃The mass-to-volume ratio of (2) is 90 μ L: 1.5 g: 0.575 g-3.45 g: 12-48 mg.

5. The method according to any one of claims 1 to 4, wherein the calcination in step (4) is 400 to 650 ℃ for 4 to 8 hours.

6. The copper oxide doped tin antimony oxide electrode prepared by the method of any one of claims 1 to 5.

7. The use of the copper oxide doped tin antimony oxide electrode of claim 6 for degrading phenolic organics or dye-like species in organic wastewater.

8. The titanium-based ultrasonic copper plating method is characterized by comprising the following steps:

9. A method of preparing a tin monolayer comprising the steps of:

(3) chemical deposition of tin and antimony: preparing solution A and solution B, wherein the solution A contains thiourea, acetic acid, sodium dihydrogen phosphate, OP-10 and polyethylene glycol; the solution B contains sulfuric acid, citric acid and tin salt; then placing the activated titanium substrate into a mixed solution of A, B liquid for chemical deposition to obtain a titanium substrate after chemical tin plating of a simple substance; wherein the mass volume ratio of the sulfuric acid to the citric acid to the tin salt in the solution B is 90 mu L: 1.5 g: 0.575 g-3.45 g.

10. A method for preparing an antimony monolayer, comprising the steps of:

(3) chemical deposition of tin and antimony: preparing solution A and solution B, wherein the solution A contains thiourea, acetic acid, sodium dihydrogen phosphate, OP-10 and polyethylene glycol; the solution B contains sulfuric acid, citric acid and SbCl₃(ii) a Then putting the activated titanium substrate into the mixed solution of A, B liquid for chemical deposition to obtain the titanium substrate after chemical antimony plating; wherein the solution B contains sulfuric acid, citric acid and SbCl₃The mass-to-volume ratio of (a) is 90 uL: 1.5 g: 12-48 mg.