CN106167290A - A kind of rare earth Ce doping Ti/Sb SnO2the preparation method of electrode - Google Patents

A kind of rare earth Ce doping Ti/Sb SnO2the preparation method of electrode Download PDF

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CN106167290A
CN106167290A CN201610710298.4A CN201610710298A CN106167290A CN 106167290 A CN106167290 A CN 106167290A CN 201610710298 A CN201610710298 A CN 201610710298A CN 106167290 A CN106167290 A CN 106167290A
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杨梅
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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
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    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46133—Electrodes characterised by the material
    • C02F2001/46138—Electrodes comprising a substrate and a coating
    • C02F2001/46142—Catalytic coating
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract

The invention discloses a kind of rare earth Ce doping Ti/Sb SnO2Electrode and preparation method thereof.Described rare earth Ce doping Ti/Sb SnO2Electrode includes titanio sheet, the Ti/Sb SnO formed at titanio sheet surface-coated masking liquid rear oxidation2Layer and at Ti/Sb SnO2Layer surface repeatedly coats Ce active layer and forms the Ti/Sb SnO of Ce doping2Electrode, its preparation method includes the preparation of Ti electrode, Ti/Sb SnO2The preparation of electrode, Ce adulterate Ti/Sb SnO2The steps such as the preparation of electrode.The present invention utilizes the special atomic structure of rare earth element ce and compound thereof to have special optical, electrical a, magnetic property and its higher heat stability improves catalysis activity and the current efficiency of electrode.

Description

A kind of rare earth Ce doping Ti/Sb-SnO2The preparation method of electrode
Technical field
The invention belongs to chemical electrode and preparing technical field thereof, be specifically related to a kind of rare earth Ce doping Ti/Sb-SnO2Electricity Pole and preparation method thereof.
Background technology
Chemically modified electrode (CME) be grow up one of the mid-1970s emerging, be also the most active Electrochemistry and the Disciplinary Frontiers of Electroanalytical Chemistry.Chemically modified electrode is the electrode made by conductor or quasiconductor, applies on surface The thin film with selective chemical group of monomolecular, polymolecular, ion or polymer is (from unimolecule to several Micron), present the chemistry of this modified membrane, the character of electrochemistry by means of Faraday (consumption electric charge) reaction.Pass through covalency Key, adsorb, the means such as polymerization are on purpose entered and are drawn by the material with functional (such as: chemistry, electrochemistry, optics etc.) Entering electrode surface, make electrode give chemical modification new, that specific process is referred to as electrode, obtained electrode referred to as chemistry is repaiied Decorations electrode.
Ti-base Sn-Sb coated electrode causes researcher with its good behaviour in terms of processing difficult biological fall organic wastewater Extensive concern, research shows, adulterate in Ti-base Sn-Sb coated electrode some special metal or nonmetalloids, not only may be used To change electric conductivity and the stability of electrode, and can affect the electro catalytic activity of electrode, rare earth element is special due to it 4f electron structure, has physics and the chemical property of uniqueness.The most studied confirmation of catalytic performance of rare earth element also extensively should In the preparation of various catalyst.But, both at home and abroad rare earth is applied the development of electro catalytic electrode in electro-chemical water processes Aspect is the most little.
Summary of the invention
In order to overcome the deficiencies in the prior art, it is an object of the invention to provide a kind of rare earth Ce doping Ti/Sb-SnO2Electricity Pole, utilizes the special atomic structure of rare earth element ce and compound thereof to have special optical, electrical, magnetic property and its higher heat Stability improves catalysis activity and the current efficiency of electrode.
For solving the problems referred to above, the technical solution adopted in the present invention is as follows:
A kind of rare earth Ce doping Ti/Sb-SnO2Electrode, including titanio sheet, in titanio sheet surface-coated masking liquid rear oxidation shape The Ti/Sb-SnO become2Layer and at Ti/Sb-SnO2Layer surface coats the Ti/Sb-SnO of the Ce doping that Ce active layer is formed repeatedly2 Electrode.
Rare earth Ce doping Ti/Sb-SnO of the present invention2In electrode, further scheme, described masking liquid is to use SnCl4·5H2O and SbCl3Being that raw material is prepared from ethylene glycol, citric acid, its preparation method is as follows: first by ethylene glycol and lemon Lemon acid reaction prepares the alcoholic solution of ethylene glycol citrate, is subsequently adding SnCl4·5H2O and SbCl3, stir and be warming up to 85- 95 DEG C, constant temperature 25-35 minute.
Rare earth Ce doping Ti/Sb-SnO of the present invention2In electrode, further scheme, the amount of the material of ethylene glycol: The amount of the material of citric acid: SnCl4·5H2O and SbCl3The amount sum of material be 14:3:1, described SnCl4·5H2O and SbCl3The atom mass rate of Sn Yu Sb be 100:10.
Another object of the present invention is at rare earth Ce doping Ti/Sb-SnO a kind of with offer2The preparation method of electrode, by this Method obtains a kind of rare earth Ce doping Ti/Sb-SnO with high catalytic activity and high current efficiency2Electrode.
A kind of rare earth Ce doping Ti/Sb-SnO2The preparation method of electrode, this preparation method comprises the following steps:
1) preparation of Ti electrode: by titanio sheet sand papering, wash down with water be placed in NaOH solution be heated to boiling, Taking-up is heated to boiling with oxalic acid solution again and is etched, and i.e. obtains Ti electrode；
2)Ti/Sb-SnO2The preparation of electrode: use SnCl4·5H2O and SbCl3It is that raw material preparation is coated with ethylene glycol, citric acid Liquid, is coated in step 1 by the masking liquid of preparation) prepared by Ti electrode on, be placed in baking oven baking, then proceed in Muffle furnace roast Burn, repetitive coatings, baking and roasting 10-15 time；Finally it is placed in Muffle furnace after aoxidizing and cooling down and obtains Ti/Sb-SnO2Electrode；
3) Ce doping Ti/Sb-SnO2The preparation of electrode: by the ratio of atom mass rate 100:10:1 according to Sn:Sb:Ce Active layer be repeatedly coated in Ti/Sb-SnO2Electrode surface, forms the Ti/Sb-SnO of Ce doping2Electrode.
In above-mentioned preparation method, further scheme, step 1) in the mass concentration of NaOH solution be 3-8%, at NaOH In solution, the time of boiling is 0.5-1.2 hour；The mass concentration of oxalic acid solution is 8-12%, ebuillition of heated in oxalic acid solution Time be 1.5-2.5 hour.
In above-mentioned preparation method, further scheme, step 2) in prepare concretely comprising the following steps of masking liquid: first by ethylene glycol with Citric acid reactions prepares the alcoholic solution of ethylene glycol citrate, is subsequently adding SnCl4·5H2O and SbCl3, stir and be warming up to 85-95 DEG C, constant temperature 25-35 minute.
In above-mentioned preparation method, further scheme, the amount of the material of ethylene glycol: the amount of the material of citric acid: SnCl4· 5H2O and SbCl3The amount sum of material be 14:3:1, described SnCl4·5H2O and SbCl3The atom mass rate of Sn with Sb be 100:10。
In above-mentioned preparation method, further scheme, step 2) in the temperature of baking oven baking be 120-140 DEG C, baking Time is 8-12 minute；The temperature of Muffle furnace is 480-550 DEG C, and the time of roasting is 8-12 minute；Last oxygen in Muffle furnace The time changed is 0.8-1.2 hour.
In above-mentioned preparation method, further scheme, step 3) in repeatedly to coat the number of times of Ce active layer be 5-8 time.
Relative to prior art, beneficial effects of the present invention is as follows:
Rare earth Ce doping Ti/Sb-SnO the most of the present invention2Electrode, the true area of electrode is greatly increased, and crystal grain is tied Close tight free from flaw, can effectively stop the diffusion of nascent oxygen atom, it is to avoid high resistance type TiO2The formation of oxide-film, is conducive to prolonging Long electrode service life；
Rare earth Ce doping Ti/Sb-SnO the most of the present invention2In electrode, Ce is at SnO2Middle solid solution changes SnO2Crystal grain The ratio of formation speed and growth rate so that SnO2Particle diameter reduces, and specific surface area increases, and adds the quantity of active site, favorably In improving electro catalytic activity；
Rare earth Ce doping Ti/Sb-SnO the most of the present invention2In electrode, the addition of cerium makes electrode performance increase, Relative to Ti base electrode and Ti/Sb-SnO2Electrode, Ce adulterates Ti/Sb-SnO2The current efficiency of electrode is maximum, it is possible to more increase Efficient degradation of organic substances.
Below in conjunction with the drawings and the specific embodiments, the invention will be further described.
Accompanying drawing explanation
Fig. 1 is Ti electrode of the present invention, Ti/Sb-SnO2Electrode and the Ti/Sb-SnO of Ce doping2Three kinds of electrodes of electrode SEM schemes；Wherein (a) is the scanning electron microscope (SEM) photograph of Ti base electrode；B () is Ti/Sb-SnO2The scanning electron microscope (SEM) photograph of electrode；C () is Ce The Ti/Sb-SnO of doping2The scanning electron microscope (SEM) photograph of electrode；
Fig. 2 is the EDS figure of the Ti electrode prepared by the present invention；
Fig. 3 is the Ti/Sb-SnO prepared by the present invention2The EDS figure of electrode；
Fig. 4 is the Ti/Sb-SnO of the Ce doping prepared by the present invention2The EDS figure of electrode；
Fig. 5 is Ti electrode of the present invention, Ti/Sb-SnO2Electrode and the Ti/Sb-SnO of Ce doping2The XRD figure of electrode；Wherein A represents that Ti electrode, b represent Ti/Sb-SnO2Electrode, c represent the Ti/Sb-SnO that Ce adulterates2Electrode；
Fig. 6 is Ti electrode of the present invention, Ti/Sb-SnO2Electrode and the Ti/Sb-SnO of Ce doping2The cyclic voltammetric of electrode Figure；Wherein a represents that Ti electrode, b represent Ti/Sb-SnO2Electrode, c represent the Ti/Sb-SnO that Ce adulterates2Electrode；
Fig. 7 is Ti electrode of the present invention, Ti/Sb-SnO2Electrode and the Ti/Sb-SnO of Ce doping2Electrode is when difference is electrolysed Between solution remains the concentration map of DBP；Wherein a represents that Ti electrode, b represent Ti/Sb-SnO2Electrode, c represent the Ti/ that Ce adulterates Sb-SnO2Electrode.
Detailed description of the invention
Rare earth Ce doping Ti/Sb-SnO of the present invention2Electrode, it includes titanio sheet, is coated with in titanio sheet surface-coated The Ti/Sb-SnO that liquid rear oxidation is formed2Layer and at Ti/Sb-SnO2Layer surface coats the Ce doping of Ce active layer formation repeatedly Ti/Sb-SnO2Electrode.
Rare earth Ce doping Ti/Sb-SnO of the present invention2In electrode, further scheme, described masking liquid is to use SnCl4·5H2O and SbCl3Being that raw material is prepared from ethylene glycol, citric acid, its preparation method is as follows: first by ethylene glycol and lemon Lemon acid reaction prepares the alcoholic solution of ethylene glycol citrate, is subsequently adding SnCl4·5H2O and SbCl3, stir and be warming up to 85- 95 DEG C, constant temperature 25-35 minute.
Rare earth Ce doping Ti/Sb-SnO of the present invention2In electrode, further scheme, the amount of the material of ethylene glycol: The amount of the material of citric acid: SnCl4·5H2O and SbCl3The amount sum of material be 14:3:1, described SnCl4·5H2O and SbCl3The atom mass rate of Sn Yu Sb be 100:10.
Being the one of rare earth element due to Ce in the present invention, its atomic structure is special, and electron structure is 4f14d16s2, internal layer 4f track unpaired electron is many, and character is very active, almost can have an effect with all elements, due to it Unique f electronic configuration, its compound has special optical, electrical and magnetic property, such as: CeO2Oxidability is strong, Nature comparison Stable, water insoluble and aqueous slkali, it is insoluble in hydrochloric acid and hydrogen peroxide, heat stability higher (can keep constant when 800 DEG C).Cause The rare earth Ce doping Ti/Sb-SnO that this obtains2Electrode catalyst activity and current efficiency.
Another object of the present invention is at rare earth Ce doping Ti/Sb-SnO a kind of with offer2The preparation method of electrode, by this Method obtains a kind of rare earth Ce doping Ti/Sb-SnO with high catalytic activity and high current efficiency2Electrode.
A kind of rare earth Ce doping Ti/Sb-SnO2The preparation method of electrode, this preparation method comprises the following steps:
1) preparation of Ti electrode: by titanio sheet sand papering, wash down with water be placed in NaOH solution be heated to boiling, Taking-up is heated to boiling with oxalic acid solution again and is etched, and i.e. obtains Ti electrode；
2)Ti/Sb-SnO2The preparation of electrode: use SnCl4·5H2O and SbCl3It is that raw material preparation is coated with ethylene glycol, citric acid Liquid, is coated in step 1 by the masking liquid of preparation) prepared by Ti electrode on, be placed in baking oven baking, then proceed in Muffle furnace roast Burn, repetitive coatings, baking and roasting 10-15 time；Finally it is placed in Muffle furnace after aoxidizing and cooling down and obtains Ti/Sb-SnO2Electrode；
3) Ce doping Ti/Sb-SnO2The preparation of electrode: according to the ratio of atom mass rate 100:10:1 of Sn:Sb:Ce Active layer is coated in Ti/Sb-SnO repeatedly2Electrode surface, forms the Ti/Sb-SnO of Ce doping2Electrode.
In above-mentioned preparation method, further scheme, step 1) in the mass concentration of NaOH solution be 3-8%, preferably The mass concentration of NaOH solution is 5%；In NaOH solution, the time of boiling is 0.5-1.2 hour, preferably 1 hour；Oxalic acid is molten The mass concentration of liquid is 8-12%, and preferred concentration of oxalic acid is 10%, and in oxalic acid solution, the time of ebuillition of heated is 1.5-2.5 Hour, preferably 2 hours.
In above-mentioned preparation method, further scheme, step 2) in prepare concretely comprising the following steps of masking liquid: first by ethylene glycol with Citric acid reactions prepares the alcoholic solution of ethylene glycol citrate, is subsequently adding SnCl4·5H2O and SbCl3, stir and be warming up to 85-95 DEG C, constant temperature 25-35 minute.
In above-mentioned preparation method, further scheme, the amount of the material of ethylene glycol: the amount of the material of citric acid: SnCl4· 5H2O and SbCl3The amount sum of material be 14:3:1, described SnCl4·5H2O and SbCl3The atom mass rate of Sn with Sb be 100:10。
In above-mentioned preparation method, further scheme, step 2) in the temperature of baking oven baking be 120-140 DEG C, baking Time is 8-12 minute；The temperature of Muffle furnace is 480-550 DEG C, and the time of roasting is 8-12 minute；Last oxygen in Muffle furnace The time changed is 0.8-1.2 hour.
In above-mentioned preparation method, further scheme, step 3) in repeatedly to coat the number of times of Ce active layer be 5-8 time.
The following is part specific embodiment of the present invention, raw material, reagent and the equipment employed in following embodiment, removes All can be obtained by commercial channel outside particular determination.
Embodiment 1
A kind of rare earth Ce doping Ti/Sb-SnO2Electrode, is prepared by the following method and forms:
1) preparation of Ti electrode: by titanio sheet sand papering, wash down with water and be placed in the NaOH solution that mass fraction is 3% In be heated to seethe with excitement 1.2h, take out again with the oxalic acid solution that mass fraction is 8% be heated to seethe with excitement 2.5h be etched, i.e. obtain Ti electrode；
2)Ti/Sb-SnO2The preparation of electrode: at 60 DEG C, first prepares ethylene glycol Fructus Citri Limoniae by ethylene glycol and citric acid reactions The alcoholic solution of acid esters, is subsequently adding the SnCl that atom mass rate is 100:104·5H2O and SbCl3, ethylene glycol, citric acid, salt (SnCl4·5H2O and SbCl3) the ratio of amount of material be 14:3:1, stir and be warming up to 85 DEG C, constant temperature 350min, the most prepared Masking liquid；Masking liquid is coated uniformly on Ti electrode, in 125 DEG C of baking ovens, first keeps 12min, then proceed to the Muffle furnace of 480 DEG C Middle roasting 12min, then be coated, 10 times repeatedly, finally it is placed in Muffle furnace oxidation 0.8h furnace cooling, i.e. prepares Ti/Sb-SnO2Electrode；
3) Ce doping Ti/Sb-SnO2The preparation of electrode: by the active layer warp of atom mass rate 100:10:1 of Sn:Sb:Ce Cross 5 times and be repeatedly coated in Ti/Sb-SnO2Electrode surface forms the Ti/Sb-SnO of Ce doping2Electrode.
Embodiment 2
A kind of rare earth Ce doping Ti/Sb-SnO2Electrode, is prepared by the following method and forms:
1) preparation of Ti electrode: by titanio sheet sand papering, wash down with water and be placed in the NaOH solution that mass fraction is 5% In be heated to seethe with excitement 1h, take out again with the oxalic acid solution that mass fraction is 10% be heated to seethe with excitement 2h be etched, i.e. obtain Ti Electrode；
2)Ti/Sb-SnO2The preparation of electrode: at 60 DEG C, first prepares ethylene glycol Fructus Citri Limoniae by ethylene glycol and citric acid reactions The alcoholic solution of acid esters, is subsequently adding the SnCl that atom mass rate is 100:104·5H2O and SbCl3, ethylene glycol, citric acid, salt (SnCl4·5H2O and SbCl3) the ratio of amount of material be 14:3:1, stir and be warming up to 90 DEG C, constant temperature 30min, i.e. prepare and be coated with Liquid.It is coated uniformly on Ti electrode, in 130 DEG C of baking ovens, is first kept 10min, then proceed to the Muffle furnace of 500 DEG C roasts Burn 10min, then be coated, 12 times repeatedly, be finally placed in Muffle furnace oxidation 1.0h furnace cooling, i.e. prepare Ti/ Sb-SnO2Electrode；
3) Ce doping Ti/Sb-SnO2The preparation of electrode: by the Ce active layer of atom mass rate 100:10:1 of Sn:Sb:Ce Ti/Sb-SnO repeatedly it is coated in through 6 times2Electrode surface forms the Ti/Sb-SnO of Ce doping2Electrode.
Embodiment 3
A kind of rare earth Ce doping Ti/Sb-SnO2Electrode, is prepared by the following method and forms:
1) preparation of Ti electrode: by titanio sheet sand papering, wash down with water and be placed in the NaOH solution that mass fraction is 8% In be heated to seethe with excitement 0.8h, take out again with the oxalic acid solution that mass fraction is 12% be heated to seethe with excitement 1.5h be etched, to obtain final product To Ti electrode；
2)Ti/Sb-SnO2The preparation of electrode: at 60 DEG C, first prepares ethylene glycol Fructus Citri Limoniae by ethylene glycol and citric acid reactions The alcoholic solution of acid esters, is subsequently adding the SnCl that atom mass rate is 100:104·5H2O and SbCl3, ethylene glycol, citric acid, salt (SnCl4·5H2O and SbCl3) the ratio of amount of material be 14:3:1, stir and be warming up to 90 DEG C, constant temperature 30min, i.e. prepare and be coated with Liquid.It is coated uniformly on Ti electrode, in 135 DEG C of baking ovens, first keeps 8min, then proceed to the Muffle kiln roasting of 550 DEG C 8min, then be coated, 15 times repeatedly, finally it is placed in Muffle furnace oxidation 1.2h furnace cooling, i.e. prepares Ti/Sb- SnO2Electrode；
3) Ce doping Ti/Sb-SnO2The preparation of electrode: by the Ce active layer of atom mass rate 100:10:1 of Sn:Sb:Ce Ti/Sb-SnO repeatedly it is coated in through 8 times2Electrode surface forms the Ti/Sb-SnO of Ce doping2Electrode.
Electrode performance characterizes
1. scanning electron microscope SEM and EDS
The Ti in embodiment 2 is observed respectively with U.S. Amarry XYKY-1000B EDS type scanning electron microscope (SEM) Electrode, Ti/Sb-SnO2Electrode and the Ti/Sb-SnO of Ce doping2The surface topography of electrode, determine electrode top layer elementary composition and The atomic ratio of each element.Scanning electron microscope SEM result sees Fig. 1；Scanning electron microscope EDS result see Fig. 2-4 and Table 1.
From Fig. 1 (a) it can be seen that electrode surface after pretreatment creates a lot of cellular space, and distribution is relatively Uniformly.Test result indicate that, this structure contributes to strengthening the adhesion of Titanium base and face coat, make electrode electric conductivity and Corrosion resistance is remarkably reinforced.Fig. 1 (b) can be seen that prepared electrode surface generates one layer of oxide grain, this be due to Stannum component in coating can form Ti/Sn intermetallic compound with Titanium base, strengthens the adhesive force of matrix and active coating, with Time also to make Titanium base be difficult to oxidized, such that it is able to extend the working life of electrode, but these oxide grain sizes are divided greatly Cloth is uneven, can be made coating shedding by the diffusion of nascent oxygen atom for a long time.Display in Fig. 1 (c), adds cerium rear electrode Surface particles shape crystal grain becomes the least, makes the true area of electrode be greatly increased, and crystal grain is tightly combined free from flaw, can effectively hinder The only diffusion of nascent oxygen atom, it is to avoid high resistance type TiO2The formation of oxide-film, is conducive to extending electrode life.This explanation The refinement of appropriate cerium beneficially crystal grain makes electrode can preferably avoid electrolyte to pass through crack and aperture infiltration in the solution TiO is formed to electrode matrix2, highly beneficial to preparing of Ti-base Sn-Sb electrode.
The EDS result of 1: three kind of electrode of table
Element Ti electrode Ti/Sb-SnO2Electrode Ce adulterates Ti/Sb-SnO2Electrode
Sn 0 27.94% 33.90%
O 8.72% 60.03% 59.14%
Ti 90.56% 12.03% 6.14%
Cl 0.72% 0 0.82%
Fig. 2 is the EDS figure of Ti base electrode, can be seen that in addition to Ti possibly together with a small amount of O, it may be possible to due to pure in figure Titanium is easily oxidized when with air contact and creates a small amount of TiO2Caused.Minimal amount of Cl is to consider in experimentation Cl in the impurity brought into or masking liquid volatilizees caused the most completely.Fig. 3 shows Ti/Sb-SnO2The main component of electrode be Sn and O, Ti are also detected and illustrate that electrode coating thickness is close with the degree of depth that EDX tests or substrate titanium part is not completely covered；Right Electrode surface carries out point analysis and is not detected by element sb, and result shows in the case of low-doped (Sn:Sb=10:1), Sb with The mode replacing (displacement) or calking (gap) enters SnO2Lattice, introduces impurity energy level in forbidden band, is conducive to strengthening SnO2Half The electric conductivity of conductor material.The Ce doping Ti/Sb-SnO that Fig. 4 shows2In the EDS of electrode, main component is Sn and O equally, does not has Elements C e detected, it is considered to Ce enters SnO in the way of calking (gap)2Lattice.Table 1 shows Ti/Sb-SnO simultaneously2Electrode With Ce doping Ti/Sb-SnO2The main component of electrode is the same and content is close, illustrates that adding Ce only plays the work of crystal grain refinement With, this is consistent with SEM result.
2.X x ray diffractometer x XRD characterizes
To the Ti electrode prepared by embodiment 2, Ti/Sb-SnO2Electrode and the Ti/Sb-SnO of Ce doping2Electrode Japan Company D/max-rA of science turns target X-ray diffractometer (XRD) and determines the crystal structure of electrode coating, and experiment condition is as follows: Cu sun Pole, graphite monochromator, voltage: 45kV, electric current: 50mA, slit: DS=10, SS=1 °, RS=0.15mm, sweep limits is 150-850, scanning speed is 0.07s.Result sees Fig. 5.
The result of Fig. 5 shows: in Ti base electrode XRD figure, the diffraction maximum of 70.049 ° shows that its main component is Ti, this with The experimental result of EDS is consistent.And 2 θ are 3 diffraction maximums at 26.56 °, 33.7 ° and 51.96 ° in Ti/Sb-SnO2 electrode XRD Correspond respectively to (110), (101) and (211) crystal face of Sn, with JCP-DS standard card (card number: the 21-of Tetragonal SnO2 1250) data are consistent, and illustrate to define SnO2Crystal, belongs to Tetragonal rutile-type.It is not detected by the oxide group of element sb Point, this is probably Sb and enters SnO in the way of replacing (displacement) or calking (gap)2The reason of lattice, this divides with above power spectrum Analysis result is consistent.But element ti detected, it may be possible to electrode coating thickness is close with the degree of depth of test or substrate titanium part does not has It is completely covered.Ce adulterates Ti/Sb-SnO2XRD figure and Ti/Sb-SnO2Electrode XRD figure is basically identical, and main component is four directions Phase rutile type SnO2, simply SnO2Diffraction peak intensity corresponding to crystalline phase becomes strong and peak shape width, it is considered to be that Ce is at SnO2Middle solid solution Change SnO2The ratio of crystal grain formation speed and growth rate so that SnO2Particle diameter reduces, and specific surface area increases, it means that live Property point quantity increase, be conducive to improving electro catalytic activity.
3. cyclic voltammetric characterizes
Being circulated voltammertry with CHI660 type electrochemical workstation, saturated calomel electrode (SCE) is reference electrode, Ti Matrix is to electrode, and working electrode is respectively adopted the Ti electrode prepared by embodiment 2, Ti/Sb-SnO2Electrode and Ce doping Ti/ Sb-SnO2Electrode, effective area is 2.5cm × 2.5cm, and electrode spacing is 1.5cm, and electrolyte is 5mg/lDBP+ 0.1MNaCl, sweep limits 0～2V, sweep speed 10mV/s.Result sees Fig. 6.
The result of Fig. 6 can be seen that the oxygen evolution potential of three kinds of electrodes has significant difference, its oxygen evolution potential minimum for Ti base Body electrode 1.5v, Ce adulterate Ti/Sb-SnO2And Ti/Sb-SnO2Essentially identical all at about 1.8v, electrode occurs oxidation also While former reaction, there is the competitive reaction of water electrolysis precipitated oxygen and hydrogen, if organic oxidizing potential is less than electrode Oxygen evolution potential, before anode reaches oxygen evolution potential, Organic substance is catalyzed oxidation on anode, thus oxidation same amount During DBP, Ti base electrode is due to its oxygen evolution potential this Organic substance of little very difficult oxidation.Figure showing, Ti matrix curve ratio is shallower, this Illustrating under equilibrium potential, solution electrode interface only has minimal amount of electronics to shift, and electron transfer all changes electricity The interfacial electric double layer on surface, pole, is a process to interfacial electric double layer discharge and recharge, there is not faraday's electronic transfer process, with Sample explanation Ti base electrode is difficult to oxidation this Organic substance DBP.Contrary Ti/Sb-SnO2With Ce doping Ti/Sb-SnO2Electrode curve has The gradient and start to aoxidize DBP respectively at 1v and 1.2v (vsAg/Ag-Cl) place, and Ce adulterates Ti/Sb-SnO2The peak of anodizing Current value is significantly raised, illustrates that the addition of cerium makes electrode performance increase (consistent with the result above characterized), aoxidizes identical Ce doping Ti/Sb-SnO during DBP2The current efficiency of electrode is maximum, it is possible to degradation of organic substances more expeditiously.
4. degraded DBP test
Respectively with Ce doping Ti/Sb-SnO prepared in embodiment 22、Ti/Sb-SnO2It is anode with Ti electrode, with Ti Electrode is negative electrode, utilizes homemade electrolysis unit to carry out electrolytic experiment；Electrolyte 5mg/lDBP+0.1MNaCl, electrolyte volume 400ml, electric current density 1.6mA/cm2, electrode spacing 1.5cm, pH value is 6.89, electrode area 2.5cm × 2.5cm, and uses Moderate-speed mixer.Result sees Fig. 7.
The result of Fig. 7 shows: Ti electrode obvious DBP of 20min removal effect before electrolysis is directly dropped to by 5ppm 4.3ppm, 60min curve later becomes DBP concentration after mild electrode degrading DBP ability is decreased until 120min and no longer declines, Clearance is the lowest by only 32%.And Ti/Sb-SnO2Electrode DBP when 20min is just degraded to 4ppm effect from 5ppm and is substantially better than Ti electrode, after 180min, DBP concentration no longer changes, and clearance is higher by 8% than Ti electrode, illustrates that the addition of tin-antimony oxide is certain Improve the electro catalytic activity of Ti electrode.The Ti/Sb-SnO but Ce adulterates2Electrode DBP when 20min is just degraded to 3.5ppm, catalytic performance further enhances, and the curve DBP concentration after 180min that tends towards stability keeps constant after 90min, removes Rate reaches 60%.Will become apparent from Ce doping Ti/Sb-SnO2The current efficiency of electrode is much higher than two above electrode, this with The result of upper sign matches.But it is relatively low caused that consideration that DBP clearance is on the low side is applying current intensity.
Reach a conclusion as follows by above-mentioned characterization result:
1) scanning electron microscope SEM and EDS result show, tin antimony oxide coated addition makes Titanium base surface area Increased catalysis increased activity, but crystal grain bigger skewness coating is insecure, after doped with cerium, crystal grain is tiny is tightly combined Free from flaw, extends the working life of electrode while increasing catalytic active center, favourable to tin antimony oxide coated electrode.
2) X-ray diffraction XRD shows, Ti/Sb-SnO2Electrode and Ce doping Ti/Sb-SnO2The main component of electrode is all The Tetragonal rutile-type SnO that catalysis activity is high2, but the addition of Ce makes SnO2Diffraction peak intensity becomes strong peak shape width so that SnO2 Particle diameter reduces, and specific surface area increases, consistent with scanning electron microscope result.
3) cyclic voltammetric result shows, tin antimony oxide coated addition makes Titanium base electrode oxygen evolution potential become big, oxygen Change performance to increase, the Ti/Sb-SnO but Ce adulterates2The peak point current of anodizing is significantly raised, and oxidizing potential diminishes, electric current Efficiency increases.
4) degraded DBP the results show, the addition of tin-antimony oxide makes the electro catalytic activity of Ti electrode strengthen going of DBP Except rate increased, the Ti/Sb-SnO but Ce adulterates2Electrode electro catalytic activity is remarkably reinforced, and DBP clearance reaches 60%, this with The result more than characterized matches.
Above-mentioned embodiment is only the preferred embodiment of the present invention, it is impossible to limit the scope of protection of the invention with this, The change of any unsubstantiality that those skilled in the art is done on the basis of the present invention and replacement belong to institute of the present invention Claimed scope.

Claims (9)

1. a rare earth Ce doping Ti/Sb-SnO2Electrode, it is characterised in that it includes titanio sheet, is coated with in titanio sheet surface-coated The Ti/Sb-SnO that liquid rear oxidation is formed2Layer and at Ti/Sb-SnO2Layer surface coats the Ce doping of Ce active layer formation repeatedly Ti/Sb-SnO2Electrode.
Rare earth Ce doping Ti/Sb-SnO the most according to claim 12Electrode, it is characterised in that described masking liquid is to use SnCl4·5H2O and SbCl3Being that raw material is prepared from ethylene glycol, citric acid, its preparation method is as follows: first by ethylene glycol and lemon Lemon acid reaction prepares the alcoholic solution of ethylene glycol citrate, is subsequently adding SnCl4·5H2O and SbCl3, stir and be warming up to 85- 95 DEG C, constant temperature 25-35 minute.
Rare earth Ce doping Ti/Sb-SnO the most according to claim 22Electrode, it is characterised in that wherein, the material of ethylene glycol Amount: the amount of the material of citric acid: SnCl4·5H2O and SbCl3The amount sum of material be 14:3:1, described SnCl4·5H2O And SbCl3The atom mass rate of Sn Yu Sb be 100:10.
4. a rare earth Ce doping Ti/Sb-SnO as claimed in claim 12The preparation method of electrode, it is characterised in that this system Preparation Method comprises the following steps:
1) preparation of Ti electrode: by titanio sheet sand papering, wash down with water be placed in NaOH solution be heated to boiling, take out It is heated to boiling with oxalic acid solution again to be etched, i.e. obtains Ti electrode；
2)Ti/Sb-SnO2The preparation of electrode: use SnCl4·5H2O and SbCl3It is that masking liquid prepared by raw material with ethylene glycol, citric acid, will The masking liquid of preparation is coated in step 1) prepared by Ti electrode on, be placed in baking oven baking, then proceed to Muffle kiln roasting, heavily Overcoating covers, toast and roasting 10-15 time；Finally it is placed in Muffle furnace after aoxidizing and cooling down and obtains Ti/Sb-SnO2Electrode；
3) Ce doping Ti/Sb-SnO2The preparation of electrode: by the work of the ratio of atom mass rate 100:10:1 according to Sn:Sb:Ce Property layer is coated in Ti/Sb-SnO repeatedly2Electrode surface, forms the Ti/Sb-SnO of Ce doping2Electrode.
Preparation method the most according to claim 4, it is characterised in that step 1) in the mass concentration of NaOH solution be 3- 8%, in NaOH solution, the time of boiling is 0.5-1.2 hour；The mass concentration of oxalic acid solution is 8-12%, at oxalic acid solution The time of middle ebuillition of heated is 1.5-2.5 hour.
Preparation method the most according to claim 4, it is characterised in that step 2) in prepare concretely comprising the following steps of masking liquid: first Ethylene glycol and citric acid reactions are prepared the alcoholic solution of ethylene glycol citrate, is subsequently adding SnCl4·5H2O and SbCl3, stirring And it is warming up to 85-95 DEG C, constant temperature 25-35 minute.
Preparation method the most according to claim 6, it is characterised in that wherein, the amount of the material of ethylene glycol: the thing of citric acid The amount of matter: SnCl4·5H2O and SbCl3The amount sum of material be 14:3:1, described SnCl4·5H2O and SbCl3Sn and Sb Atom mass rate be 100:10.
Preparation method the most according to claim 4, it is characterised in that step 2) in baking oven baking temperature be 120-140 DEG C, the time of baking is 8-12 minute；The temperature of Muffle furnace is 480-550 DEG C, and the time of roasting is 8-12 minute；Last horse Not in stove, the time of oxidation is 0.8-1.2 hour.
Preparation method the most according to claim 4, it is characterised in that step 3) in repeatedly coat the number of times of Ce active layer and be 5-8 time.
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CN108046380A (en) * 2017-12-13 2018-05-18 东华大学 A kind of titanium-based Sn-Sb-Ce oxide electrodes and its preparation method and application
CN108385132A (en) * 2018-03-09 2018-08-10 三峡大学 A kind of Co doping MoS2The CVD preparation methods of array original position electrode
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CN108517534B (en) * 2018-03-09 2020-06-23 三峡大学 CVD method for preparing multifunctional nickel-doped molybdenum disulfide in-situ electrode
CN113636625A (en) * 2021-08-09 2021-11-12 中国科学院南京土壤研究所 Electrode capable of self-generating oxidant and preparation method and application thereof
CN113636625B (en) * 2021-08-09 2022-04-29 中国科学院南京土壤研究所 Electrode capable of self-generating oxidant and preparation method and application thereof
CN113800604A (en) * 2021-08-16 2021-12-17 常州大学 Graphene-rare earth gadolinium co-doped Ti/SnO2-Sb composite electrode and preparation method thereof

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