CN107804900A - A kind of steady photovoltaic electrodes of titanium-based type and its preparation method and application - Google Patents
A kind of steady photovoltaic electrodes of titanium-based type and its preparation method and application Download PDFInfo
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Abstract
The invention provides a kind of steady photovoltaic electrodes of titanium-based type and its preparation method and application, in traditional SnO2On the basis of Sb/Ti electrodes, the Sn Sb Ti active layers of plating nanometer Ag/AgCl doping, Ag/AgCl plasma effects, TiO are utilized2Photoelectrocatalysis characteristic and Sn Sb and the solid-solution characteristics in intermediate layer, prepare Sn Sb Ag Ti/SnO2Sb/Ti photoelectrocatalysielectrode electrodes, this method life have the advantages that production. art is simple, easily operated, easily realize large-scale industrial production.The steady photovoltaic electrodes of titanium-based type provided herein, have the advantages that processing cost is low, technique is simple, catalytic performance is high, service life is long, and the more traditional SnO of the electrode2Sb/Ti electrodes have higher electro catalytic activity and relatively low background potential, and electrode active surface layer realizes photochemical catalytic oxidation and the collaboration of electrocatalytic oxidation organic pollution is decomposed and removed.
Description
Technical field
The present invention relates to the preparation of the steady electrode of titanium-based type and the photoelectricity efficient catalytic processing technology field of organic wastewater, specifically
For, it is related to a kind of steady photovoltaic electrodes of titanium-based type and its preparation method and application.
Background technology
Industrial organic waste water from fields such as food processing, process hides, coking, pharmacy, DYE PRODUCTIONs is because of its pollutant
Concentration is high, molecular weight is big, the characteristic of difficult for biological degradation, turns into one of difficult point of current field of waste water treatment, efficiently and inexpensive
Administer high concentration organic polluting water has turned into the focal issue of domestic and international environmental worker's common concern.Electro-catalytic oxidation technology
One kind of high-level oxidation technology, the technology utilization electrode under overpotential for oxygen evolution hydroxyl radical free radical caused by electrolysis water and realize
The oxidation mineralising of useless Organic substance in water or conversion are decomposed, and are had organic pollutant removal efficiency high, floor space small and are easy to certainly
The characteristics of dynamicization controls.The design of electrode and the heart that preparation is electro-catalytic oxidation technology, are directly connected to electric catalysis reactor
The widow crowd and the height of efficiency that hydroxyl radical free radical expedites the emergence of.
, the problems such as high processing costs, complex process, catalytic performance are weak, service life is short be present in existing catalysis electrode.
In view of this, it is special to propose the present invention.
The content of the invention
The first object of the present invention is to provide a kind of preparation method of the steady photovoltaic electrodes of titanium-based type, to solve above-mentioned ask
Topic, the electrode is in traditional SnO2On the basis of-Sb/Ti electrodes, the Sn-Sb-Ti active layers of plating nanometer Ag/AgCl doping, profit
With Ag/AgCl plasma effects, TiO2Photoelectrocatalysis characteristic and Sn-Sb and the solid-solution characteristics in intermediate layer, system
Standby Sn-Sb-Ag-Ti/SnO2- Sb/Ti photoelectrocatalysielectrode electrodes.This method simple production process, easily operated, Yi Shi
Existing large-scale industrial production.
The second object of the present invention is to provide prepared by a kind of preparation method of the described steady photovoltaic electrodes of titanium-based type
The steady photovoltaic electrodes of titanium-based type, have the advantages that processing cost is low, technique is simple, catalytic performance is high, service life is long, and the electricity
The more traditional SnO in pole2- Sb/Ti electrodes have higher electro catalytic activity and relatively low background potential, and electrode active surface layer is real
Photochemical catalytic oxidation is showed and the collaboration of electrocatalytic oxidation organic pollution is decomposed and removed.
The third object of the present invention is to provide prepared by a kind of preparation method of the described steady photovoltaic electrodes of titanium-based type
Application of the steady photovoltaic electrodes of titanium-based type in photoelectrocatalysis organic wastewater, realizes photochemical catalytic oxidation and the organic dirt of electrocatalytic oxidation
Removal is decomposed in the collaboration for contaminating thing.
In order to realize the above-mentioned purpose of the present invention, spy uses following technical scheme：
A kind of preparation method of the steady photovoltaic electrodes of titanium-based type, comprises the following steps：
(1) preparation of Sn-Sb-Ag-Ti composite precursors：Stannic chloride pentahydrate and antimony trichloride are dissolved in butyl titanate
Concentrated hydrochloric acid is added dropwise in organic solvent, while stirring, is then added in the mixed solution of absolute ethyl alcohol and concentrated hydrochloric acid, disperses equal
It is even, then by the Ag/AgCl photocatalytic nanometer particles of preparation according to Sn:Sb:Ti:Ag mol ratio 9:1:(2-6):(0.1-
0.4) ratio is added into above-mentioned solution and stirred, and obtains Sn-Sb-Ag-Ti composite precursors；
Preferably, the Sn:Sb:Ti:Ag mol ratio is 9:1:4:0.1；
(2)Sn-Sb-Ag-Ti/SnO2The preparation of the steady photovoltaic electrodes of-Sb/Ti types：Photoelectricity electricity is prepared using sol-gel process
Pole, preparation-obtained composite precursor in step (1) is evenly coated in SnO2On the steady electrode of-Sb/Ti types, obtained intermediate
It is placed in baking oven and dries, under nitrogen protection, high temperature sintering is carried out at 450-600 DEG C finally.
The method of the steady photovoltaic electrodes of preparation titanium-based type provided herein, using metal titanium sheet as substrate, coating semiconductor
Metal oxide, regulated and controled by the Combination Design and preparation technology parameter of photoelectrocatalysimaterial material, prepare that cost is cheap, production work
Skill is simple, and possesses the electrode type of electrical enhanced photocatalysis characteristic.
Preferably, in step (1), in the mixed solution of the absolute ethyl alcohol and concentrated hydrochloric acid, the absolute ethyl alcohol with
The volume ratio of the concentrated hydrochloric acid is (90-100):4；More preferably 90:4.
Preferably, in step (2), the high temperature sintering, following steps are specifically included：
From 0 DEG C to the 198-202 DEG C 30-35min that heats up, 50-70 minutes are incubated at 198-202 DEG C, are then risen in 40min
Temperature is incubated 50-70 minutes to 450-600 DEG C at 450-600 DEG C, repeats more than 8-9 times and operates, after cooling, obtains the titanium
The steady photovoltaic electrodes of fundamental mode；
It is furthermore preferred that from 0 DEG C to 198-202 DEG C heating 30-35min, 50-70 minutes are incubated at 198-202 DEG C, Ran Hou
500-550 DEG C is warming up in 40min, and 50-70 minutes are incubated at 500-550 DEG C, more than 8-9 times is repeated and operates, after cooling,
Obtain the steady photovoltaic electrodes of titanium-based type.
Preferably, in step (1), the preparation method of the Ag/AgCl photocatalytic nanometers particle, following step is specifically included
Suddenly：By AgNO3Add in ammoniacal liquor, then constant volume is diluted with deionized water, add concentrated hydrochloric acid after stirring evenly, be stirred vigorously, formed uniform
Suspension, the suspension is mixed with absolute ethyl alcohol, be aerated and add light irradiation simultaneously, after centrifugation, rushed using deionized water
Wash, be dried at room temperature for constant weight, obtain the Ag/AgCl photocatalytic nanometer particles；
Wherein, the AgNO3Mass ratio with the ammoniacal liquor is 1:(9-10), preferably 1:9.97；The AgNO3With institute
The mass ratio for stating concentrated hydrochloric acid is 1：(8.4-8.6), preferably 1:8.42；
It is furthermore preferred that the time of the stirring is 22-26h.
Preferably, the volume of the absolute ethyl alcohol and the volume ratio after the dilution constant volume with deionized water are (0.9-
1.0)：1.
Preferably, described plus light irradiation time is 50-70 minutes.
Preferably, in step (2), it is placed in described in baking oven during drying, the temperature of the drying is 100-
120 DEG C, the time of the preferred drying is 20-30min.
Preferably, in step (2), the SnO2The preparation method of the steady electrode of-Sb/Ti types, specifically includes following steps：
On the titanium electrode of etched processing, the n-butanol presoma of stannic chloride pentahydrate and antimony trichloride is brushed,
The mol ratio of tin and antimony is 9 in presoma:1, dried after brushing, 10-15min is then calcined at 540-560 DEG C, repeat to dry
Two are operated 8-9 times with calcining, and the SnO is obtained after natural cooling2The steady electrode of-Sb/Ti types；
It is furthermore preferred that the calcining is operated using Muffle furnace；
It is furthermore preferred that the temperature of the drying is 100-120 DEG C, the time of drying is 20-25min；Still more preferably
, the drying is operated using air dry oven.
The steady photovoltaic electrodes of titanium-based type prepared by the preparation method of the described steady photovoltaic electrodes of titanium-based type.
The steady photovoltaic electrodes of titanium-based type prepared by the preparation method of the described steady photovoltaic electrodes of titanium-based type have in photoelectrocatalysis
Application in machine waste water.
Compared with prior art, beneficial effects of the present invention are：
(1) preparation method of the steady photovoltaic electrodes of titanium-based type provided herein, in traditional SnO2The base of-Sb/Ti electrodes
On plinth, the Sn-Sb-Ti active layers of plating nanometer Ag/AgCl doping, Ag/AgCl plasma effects, TiO are utilized2Photoelectricity urge
Change characteristic and Sn-Sb and the solid-solution characteristics in intermediate layer, prepare Sn-Sb-Ag-Ti/SnO2- Sb/Ti photoelectrocatalysielectrode electrodes, this method
Life has the advantages that production. art is simple, easily operated, easily realizes large-scale industrial production.
(2) the steady photovoltaic electrodes of titanium-based type provided herein, have processing cost is low, technique is simple, catalytic performance is high,
The advantages that service life is long, and electrode tradition SnO2- Sb/Ti electrodes have higher electro catalytic activity and relatively low background
Potential, and electrode active surface layer realizes photochemical catalytic oxidation and the collaboration of electrocatalytic oxidation organic pollution is decomposed and removed.
Brief description of the drawings
, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical scheme of the prior art
The required accompanying drawing used is briefly described in embodiment or description of the prior art, it should be apparent that, in describing below
Accompanying drawing is some embodiments of the present invention, for those of ordinary skill in the art, before creative work is not paid
Put, other accompanying drawings can also be obtained according to these accompanying drawings.
The Sn-Sb-Ag-Ti/SnO that Fig. 1 is provided by the embodiment of the present invention 12The steady electrode of-Sb/Ti types and traditional SnO2-Sb/
The comparison diagram of the steady electrode surface pattern of Ti types；
The Sn-Sb-Ag-Ti/SnO that Fig. 2 is provided by the embodiment of the present invention 12The steady electrode of-Sb/Ti types and traditional SnO2-Sb/
The steady electrode power spectrum comparison diagram of Ti types；
The Sn-Sb-Ag-Ti/SnO that Fig. 3 is provided by the embodiment of the present invention 12The steady electrode of-Sb/Ti types and traditional SnO2-Sb/
The steady electrode AC impedance test comparison figure of Ti types；
The Sn-Sb-Ag-Ti/SnO that Fig. 4 is provided by invention embodiment 12The steady electrode of-Sb/Ti types and tradition
SnO2The steady electrode accelerating lifetime testing comparison diagram of-Sb/Ti types；
The Sn-Sb-Ag-Ti/SnO that Fig. 5 is provided by invention embodiment 12The steady electrode of-Sb/Ti types and tradition
SnO2The steady electrode of-Sb/Ti types handles phenol concentration and waste water TOC change comparison diagrams in electrocatalytic oxidation phenol wastewater；
The Sn-Sb-Ag-Ti/SnO that Fig. 6 is provided by invention embodiment 12The steady electrode of-Sb/Ti types gives up containing phenol
Water power and photoelectrocatalysioxidization oxidization phenolic wastewater treatment phenol concentration and waste water TOC change comparison diagrams.
Embodiment
Technical scheme is clearly and completely described below in conjunction with the drawings and specific embodiments, but
Be it will be understood to those of skill in the art that following described embodiment is part of the embodiment of the present invention, it is rather than whole
Embodiment, the present invention is merely to illustrate, and is not construed as limiting the scope of the present invention.Based on the embodiment in the present invention, ability
The every other embodiment that domain those of ordinary skill is obtained under the premise of creative work is not made, belongs to guarantor of the present invention
The scope of shield.Unreceipted actual conditions person in embodiment, the condition suggested according to normal condition or manufacturer are carried out.Agents useful for same
Or the unreceipted production firm person of instrument, it is the conventional products that can be obtained by commercially available purchase.
A kind of preparation method of the steady photovoltaic electrodes of titanium-based type, comprises the following steps：
(1) preparation of Sn-Sb-Ag-Ti composite precursors：Stannic chloride pentahydrate and antimony trichloride are dissolved in butyl titanate
Concentrated hydrochloric acid is added dropwise in organic solvent, while stirring, is then added in the mixed solution of absolute ethyl alcohol and concentrated hydrochloric acid, disperses equal
It is even, then by the Ag/AgCl photocatalytic nanometer particles of preparation according to Sn:Sb:Ti:Ag mol ratio 9:1:(2-6):(0.1-
0.4) ratio is added into above-mentioned solution and stirred, and obtains Sn-Sb-Ag-Ti composite precursors；
Preferably, the Sn:Sb:Ti:Ag mol ratio is 9:1:4:0.1；
(2)Sn-Sb-Ag-Ti/SnO2The preparation of the steady photovoltaic electrodes of-Sb/Ti types：Photoelectricity electricity is prepared using sol-gel process
Pole, preparation-obtained composite precursor in step (1) is evenly coated in SnO2On the steady electrode of-Sb/Ti types, obtained intermediate
It is placed in baking oven and dries, under nitrogen protection, high temperature sintering is carried out at 450-600 DEG C finally.
Photocatalysis oxidation technique under the conditions of ultraviolet irradiation, produces hole and electronics, shape using metal oxide semiconductor
Hydroxyl radical free radical is produced into photoelectric current electrolysis water and realizes the catalysis oxidation of organic matter, has that reaction condition is gentle, processing cost
The characteristics of low, but treatment of Organic Wastewater degree is low.Photoelectrocatalysis treatment of Organic Wastewater, there is advanced oxidation organic matter removal effect
Well, the characteristics of space-time yield is high, the light and electrochemical properties of material are played, so as to further improve catalytic organism efficiency and have
Effect reduces cost for wastewater treatment.
The method of the steady photovoltaic electrodes of preparation titanium-based type provided herein, in traditional SnO2The basis of-Sb/Ti electrodes
On, the Sn-Sb-Ti active layers of coating nanometer Ag/AgCl doping, utilize Ag/AgCl plasma effects, TiO2Light, electricity urges
Change characteristic and Sn-Sb and the solid-solution characteristics in intermediate layer, prepare Sn-Sb-Ag-Ti/SnO2-Sb/Ti photoelectrocatalysielectrode electrodes.Prepare
Electrode, more traditional SnO2- Sb/Ti electrodes have higher electro catalytic activity and relatively low background potential, and electrode active surface
Layer realizes photochemical catalytic oxidation and the collaboration of electrocatalytic oxidation organic pollution is decomposed and removed.
It is related to proportioning, the procedural control of preparation temperature and the manufacturing procedure of active layer material components in the preparation process of electrode, it is molten
Glue-Gel Precursor Sn-Sb-Ti-Ag mol ratio is 9:1:4:0.1, the procedural temperature control under being protected using nitrogen is sintered, shape
Into orientation SnO2And TiO2Crystal formation, while oxidations of the Ag to AgO is prevented, realize the controlled syntheses of each thing phase.Based on the above
Preparation shaping and the high catalytic activity of the steady photovoltaic electrodes of the type are realized in control and optimization.
Aforementioned proportion 9:1 is traditional SnO2- Sb/Ti electrodes are set, and widely used；Ti and Ag is in this patent
Photovoltaic electrodes prepare what is voluntarily controlled, and the control of titanium ratio is in 2-6 scopes, but 4 is best, and fixed titanium discusses well Ag doping,
0.1-0.4, maximally effective doping is 0.1, and the increase of follow-up Ag amounts can not realize the increase of electrode surface Ag contents, preparation processing
Electrode there is very similar electrochemical Characterization characteristic and PhotoelectrocatalytiPerformance Performance.
Preferably, in step (1), in the mixed solution of the absolute ethyl alcohol and concentrated hydrochloric acid, the absolute ethyl alcohol with
The volume ratio of the concentrated hydrochloric acid is (90-100):4；More preferably 90:4.
Appropriate concentrated hydrochloric acid is added in absolute ethyl alcohol, is to prevent butter of tin and the aerial hydrolysis of antimony trichloride
And generate its hydrate.
Preferably, in step (2), the high temperature sintering, following steps are specifically included：
From 0 DEG C to the 198-202 DEG C 30-35min that heats up, 50-70 minutes are incubated at 198-202 DEG C, are then risen in 40min
Temperature is incubated 50-70 minutes to 450-600 DEG C at 450-600 DEG C, repeats more than 8-9 times and operates, after cooling, obtains the titanium
The steady photovoltaic electrodes of fundamental mode；
It is furthermore preferred that from 0 DEG C to 198-202 DEG C heating 30-35min, 50-70 minutes are incubated at 198-202 DEG C, Ran Hou
500-550 DEG C is warming up in 40min, and 50-70 minutes are incubated at 500-550 DEG C, more than 8-9 times is repeated and operates, after cooling,
Obtain the steady photovoltaic electrodes of titanium-based type.
Preferably, in step (1), the preparation method of the Ag/AgCl photocatalytic nanometers particle, following step is specifically included
Suddenly：By AgNO3Add in ammoniacal liquor, then constant volume is diluted with deionized water, add concentrated hydrochloric acid after stirring evenly, be stirred vigorously, formed uniform
Suspension, the suspension is mixed with absolute ethyl alcohol, be aerated and add light irradiation simultaneously, after centrifugation, rushed using deionized water
Wash, be dried at room temperature for constant weight, obtain the Ag/AgCl photocatalytic nanometer particles；
Wherein, the AgNO3Mass ratio with the ammoniacal liquor is 1:(9-10), preferably 1:9.97；The AgNO3With institute
The mass ratio for stating concentrated hydrochloric acid is 1：(8.4-8.6), preferably 1:8.42；
It is furthermore preferred that the time of the stirring is 22-26h.
Preferably, the volume of the absolute ethyl alcohol and the volume ratio after the dilution constant volume with deionized water are (0.9-
1.0)：1.
Preferably, described plus light irradiation time is 50-70 minutes.
Preferably, in step (2), it is placed in described in baking oven during drying, the temperature of the drying is 100-
120 DEG C, the time of the preferred drying is 20-30min.
Preferably, in step (2), the SnO2The preparation method of the steady electrode of-Sb/Ti types, specifically includes following steps：
On the titanium electrode of etched processing, the n-butanol presoma of stannic chloride pentahydrate and antimony trichloride is brushed,
The mol ratio of tin and antimony is 9 in presoma:1, dried after brushing, 10-15min is then calcined at 540-560 DEG C, repeat to dry
Two are operated 8-9 times with calcining, and the SnO is obtained after natural cooling2The steady electrode of-Sb/Ti types；
It is furthermore preferred that the calcining is operated using Muffle furnace；
It is furthermore preferred that the temperature of the drying is 100-120 DEG C, the time of drying is 20-25min；Still more preferably
, the drying is operated using air dry oven.
The steady photovoltaic electrodes of titanium-based type prepared by the preparation method of the described steady photovoltaic electrodes of titanium-based type.
The steady photovoltaic electrodes of titanium-based type prepared by the preparation method of the described steady photovoltaic electrodes of titanium-based type have in photoelectrocatalysis
Application in machine waste water.
Embodiment 1
(1) traditional SnO2The preparation of the steady electrode of-Sb/Ti types：On the titanium electrode of etched processing, crystallization four is brushed
The n-butanol presoma of stannic chloride and antimony trichloride, the mol ratio of tin and antimony is 9 in presoma:1, it is put into forced air drying after brushing
20min is dried in 110 DEG C in case, 550 DEG C of calcining 10min in Muffle furnace is then transferred to, repeats two above and operate 8 times, it is natural
Taken out after cooling standby；
(2) preparation of nanometer Ag/AgCl photochemical catalysts：By 0.21g AgNO3It is put into 2.3ml 25% ammoniacal liquor, then
50ml is diluted to deionized water, and is stirred；1.5mL concentrated hydrochloric acids are added in mixed liquor, are stirred vigorously 24h, are formed uniform
Suspension；Above solution mixes with 50mL absolute ethyl alcohols, is aerated and adds light irradiation 1h simultaneously；With centrifuge precipitation and separation, spend
Ionized water rinses 4-5 times, is dried at room temperature for constant weight；
(3) preparation of Sn-Sb-Ag-Ti composite precursors：Stannic chloride pentahydrate and antimony trichloride are dissolved in butyl titanate
In organic solvent (1.5mL), quickly stir and concentrated hydrochloric acid preventing and treating butter of tin hydrolysis is added dropwise, then added to absolute ethyl alcohol
In (90mL) and concentrated hydrochloric acid (4mL) mixed solution, ultrasonic mixing is uniform, by the Ag/AgCl photocatalytic nanometers particle of preparation according to
Sn:Sb:Ti:Ag mol ratios 9:1:4:0.1 ratio is added into above-mentioned solution and stirred；
(4) the steady photovoltaic electrodes of Sn-Sb-Ag-Ti/SnO2-Sb/Ti types are prepared using sol-gel process：The forerunner that will be prepared
Body is uniformly coated in SnO2On-Sb/Ti types are steady, obtained intermediate is placed in baking oven in 110 DEG C of baking ovens and dries 20min, with
After be transferred in atmosphere furnace high temperature sintering under nitrogen protection；
Heat treatment process is as follows：0 DEG C to 200 DEG C, heat up 30min；1h is incubated at 200 DEG C, then from 200 in 40min
DEG C rise to 500 DEG C, finally in 500 DEG C of temperature lower calcination 1h, repeat more than operation 8 times, taken out after natural cooling, that is, obtain this
Photovoltaic electrodes in application.
Embodiment 2
(1) traditional SnO2The preparation of the steady electrode of-Sb/Ti types：On the titanium electrode of etched processing, crystallization four is brushed
The n-butanol presoma of stannic chloride and antimony trichloride, the mol ratio of tin and antimony is 9 in presoma:1, it is put into forced air drying after brushing
25min is dried in 100 DEG C in case, 540 DEG C of calcining 15min in Muffle furnace is then transferred to, repeats two above and operate 9 times, it is natural
Taken out after cooling standby；
(2) preparation of nanometer Ag/AgCl photochemical catalysts：By 0.22g AgNO3It is put into 2.4ml 25% ammoniacal liquor, then
45ml is diluted to deionized water, and is stirred；1.6mL concentrated hydrochloric acids are added in mixed liquor, are stirred vigorously 22h, are formed uniform
Suspension；Above solution mixes with 50mL absolute ethyl alcohols, is aerated and adds light irradiation 1h simultaneously；With centrifuge precipitation and separation, spend
Ionized water rinses 4-5 times, is dried at room temperature for constant weight；
(3) preparation of Sn-Sb-Ag-Ti composite precursors：Stannic chloride pentahydrate and antimony trichloride are dissolved in butyl titanate
In organic solvent (1.5mL), quickly stir and concentrated hydrochloric acid preventing and treating butter of tin hydrolysis is added dropwise, then added to absolute ethyl alcohol
In (100mL) and concentrated hydrochloric acid (4mL) mixed solution, ultrasonic mixing is uniform, by the Ag/AgCl photocatalytic nanometers particle of preparation according to
Sn:Sb:Ti:Ag mol ratios 9:1:6:0.4 ratio is added into above-mentioned solution and stirred；
(4) Sn-Sb-Ag-Ti/SnO is prepared using sol-gel process2The steady photovoltaic electrodes of-Sb/Ti types：The forerunner that will be prepared
Body is uniformly coated in SnO2On-Sb/Ti types are steady, obtained intermediate is placed in baking oven in 100 DEG C of baking ovens and dries 25min, with
After be transferred in atmosphere furnace high temperature sintering under nitrogen protection；
Heat treatment process is as follows：0 DEG C to 198 DEG C, heat up 30min；50min is incubated at 198 DEG C, then in 40min from
198 DEG C rise to 500 DEG C, finally in 500 DEG C of temperature lower calcination 50min, repeat operation 8 times above, take out, that is, obtain after natural cooling
Obtained the photovoltaic electrodes in the application.
Embodiment 3
(1) traditional SnO2The preparation of the steady electrode of-Sb/Ti types：On the titanium electrode of etched processing, crystallization four is brushed
The n-butanol presoma of stannic chloride and antimony trichloride, the mol ratio of tin and antimony is 9 in presoma:1, it is put into forced air drying after brushing
22min is dried in 120 DEG C in case, 560 DEG C of calcining 12min in Muffle furnace is then transferred to, repeats two above and operate 8 times, it is natural
Taken out after cooling standby；
(2) preparation of nanometer Ag/AgCl photochemical catalysts：By 0.21g AgNO3It is put into 2.3ml 25% ammoniacal liquor, then
50ml is diluted to deionized water, and is stirred；1.5mL concentrated hydrochloric acids are added in mixed liquor, are stirred vigorously 26h, are formed uniform
Suspension；Above solution mixes with 50mL absolute ethyl alcohols, is aerated and adds light irradiation 70min simultaneously；With centrifuge precipitation and separation, use
Deionized water rinsing 4-5 times, it is dried at room temperature for constant weight；
(3) preparation of Sn-Sb-Ag-Ti composite precursors：Stannic chloride pentahydrate and antimony trichloride are dissolved in butyl titanate
In organic solvent (1.5mL), quickly stir and concentrated hydrochloric acid preventing and treating butter of tin hydrolysis is added dropwise, then added to absolute ethyl alcohol
In (95mL) and concentrated hydrochloric acid (4mL) mixed solution, ultrasonic mixing is uniform, by the Ag/AgCl photocatalytic nanometers particle of preparation according to
Sn:Sb:Ti:Ag mol ratios 9:1:2:0.1 ratio is added into above-mentioned solution and stirred；
(4) Sn-Sb-Ag-Ti/SnO is prepared using sol-gel process2The steady photovoltaic electrodes of-Sb/Ti types：The forerunner that will be prepared
Body is uniformly coated in SnO2On-Sb/Ti types are steady, obtained intermediate is placed in baking oven in 120 DEG C of baking ovens and dries 30min, with
After be transferred in atmosphere furnace high temperature sintering under nitrogen protection；
Heat treatment process is as follows：0 DEG C to 200 DEG C, heat up 30min；70min is incubated at 202 DEG C, then in 40min from
202 DEG C rise to 600 DEG C, finally in 600 DEG C of temperature lower calcination 70min, repeat operation 9 times above, take out, that is, obtain after natural cooling
Obtained the photovoltaic electrodes in the application.
The electrode surface pattern test of experimental example 1
In Fig. 1, a, c are traditional SnO2The steady electrode of-Sb/Ti types amplifies 5000 and 15000 times of stereoscan photograph；B, d
For Sn-Sb-Ag-Ti/SnO2The steady electrode of-Sb/Ti types amplifies 5000 and 15000 times of stereoscan photograph.
As can be seen from the figure the electrode surface prepared in the application has few crack and texture, can effectively reduce
Active oxygen (O2, OH, O caused by electrocatalytic reaction process-) spread to titanium substrate, and form TiO2, cause active layer to peel off, greatly
Amplitude improves electrode life.
The power spectrum of experimental example 2 is tested
In Fig. 2, a, b are traditional SnO2The steady electrode microscopic appearance of-Sb/Ti types and corresponding surface sweep EDS analysis results；C, d are
Sn-Sb-Ag-Ti/SnO2The steady electrode microscopic appearance of-Sb/Ti types and corresponding surface sweep EDS analysis results.
As can be seen from the figure the electrode surface prepared in the application is in addition to Sn-Sb active components, and also effective preservation Ti-
Ag components, the presence of titanium dioxide can strengthen the light and electric catalyticing characteristic of electrode, and Ag/AgCl can promote electrode surface light induced electron
Transmission, improve the hydroxyl radical free radical oxidation operation efficiency expedited the emergence of.
The result of the ac impedance measurement of experimental example 3
In Fig. 3, Sn-Sb-Ag-Ti/SnO2The liquid phase contact resistance and charge transfer resistance (2.8 of the steady electrode of-Sb/Ti types
Ω and 0.7 Ω) it is much smaller than traditional SnO2The steady electrode of-Sb/Ti types (being respectively 37 Ω and 5.6 Ω), it is anti-to be advantageous to photoelectrocatalysis
The quick transmission of electric energy saving and electronics during answering, reduces cost, improves catalytic organism oxidation effectiveness.
The electrode accelerating lifetime testing of experimental example 4
The industrial lifetimes of electrode are in 0.5mol/L sulfuric acid solutions, in 4.0A/cm2Completed under current density, work as tank voltage
It is increased to 10V and thinks that electrode inactivates.As can be seen that traditional SnO in Fig. 42It is 3.8V that the steady electrode of-Sb/Ti types, which just starts from tank voltage,
Tank voltage rises to more than 10V after 14.6h；And Sn-Sb-Ag-Ti/SnO2The initial tank voltage 2.7V of the steady electrode of-Sb/Ti types is small
In traditional SnO2The steady electrode of-Sb/Ti types, and rise to 10V tank voltage used times 59.2h.Prepared photovoltaic electrodes have relatively low
Liquid resistance, and using using being much larger than traditional SnO2The steady electrode of-Sb/Ti types.The industrial lifetimes of the two be respectively 2.70a and
10.94a。
Handled in the electrocatalytic oxidation phenol wastewater of experimental example 5
Phenolic waste water concentration 100mg/L, electrode area 10cm*10cm, thickness 0.2mm, static treatment 1L simulated wastewaters, throw
The sodium sulphate for adding mass concentration 5% is electrolyte, current density 10mA/cm2, the processing of two electrode electrocatalytic oxidation phenolic waste waters
As a result as shown in Figure 5.As can be seen that Sn-Sb-Ag-Ti/SnO2Oxidation of phenol efficiency and the TOC drop of the steady electrode of-Sb/Ti types
Solution efficiency is significantly higher than SnO2The steady electrode of-Sb/Ti types.
On the basis of above-mentioned electrocatalytic oxidation, using 500W Metal halogen lamps as light source, collaboration photoelectrocatalysis processing is above-mentioned to contain phenol
Waste water, acquired results are as shown in Figure 6.Phenol photoelectrocatalysis efficiency is compared with electro-catalysis improved efficiency 15.8% in Fig. 6 a, in Fig. 6 b
Phenolic waste water photoelectrocatalysis TOC degradation efficiencies are 84.6%, and Electrocatalysis Degradation efficiency is 47.7%, lifting 36.9%.Thus, show
Sn-Sb-Ag-Ti/SnO is shown2The notable electrical enhanced photocatalysis characteristic of the steady electrode of-Sb/Ti types, and be more conducive to realize organic pollution
Thorough mineralising.
Although illustrate and describing the present invention with specific embodiment, but it will be appreciated that various embodiments above is only used
To illustrate technical scheme, rather than its limitations；It will be understood by those within the art that：Without departing substantially from this hair
In the case of bright spirit and scope, the technical scheme described in foregoing embodiments can be modified, or to wherein
Some or all of technical characteristic carries out equivalent substitution；And these are changed or are replaced, the essence of appropriate technical solution is not made
Depart from the scope of various embodiments of the present invention technical scheme；It is, therefore, intended that include belonging to the present invention in the following claims
In the range of all these substitutions and modifications.
Claims (10)
1. a kind of preparation method of the steady photovoltaic electrodes of titanium-based type, it is characterised in that comprise the following steps：
(1) preparation of Sn-Sb-Ag-Ti composite precursors：It is organic that stannic chloride pentahydrate and antimony trichloride are dissolved in butyl titanate
Concentrated hydrochloric acid is added dropwise in solvent, while stirring, is then added in the mixed solution of absolute ethyl alcohol and concentrated hydrochloric acid, is uniformly dispersed,
Then by the Ag/AgCl photocatalytic nanometer particles of preparation according to Sn:Sb:Ti:Ag mol ratio 9:1:(2-6):(0.1-0.4's)
Ratio is added into above-mentioned solution and stirred, and obtains Sn-Sb-Ag-Ti composite precursors；
Preferably, the Sn:Sb:Ti:Ag mol ratio is 9:1:4:0.1；
(2)Sn-Sb-Ag-Ti/SnO2The preparation of the steady photovoltaic electrodes of-Sb/Ti types：Photovoltaic electrodes are prepared using sol-gel process, will
Preparation-obtained composite precursor is evenly coated in SnO in step (1)2On the steady electrode of-Sb/Ti types, obtained intermediate is placed in
Dried in baking oven, under nitrogen protection, high temperature sintering is carried out at 450-600 DEG C finally.
2. the preparation method of the steady photovoltaic electrodes of titanium-based type according to claim 1, it is characterised in that in step (1),
In the mixed solution of the absolute ethyl alcohol and concentrated hydrochloric acid, the volume ratio of the absolute ethyl alcohol and the concentrated hydrochloric acid is (90-100):
4；Preferably 90:4.
3. the preparation method of the steady photovoltaic electrodes of titanium-based type according to claim 1, it is characterised in that in step (2), institute
High temperature sintering is stated, specifically includes following steps：
From 0 DEG C to the 198-202 DEG C 30-35min that heats up, 50-70 minutes are incubated at 198-202 DEG C, are then warming up in 40min
450-600 DEG C, and 50-70 minutes are incubated at 450-600 DEG C, repeat more than 8-9 times and operate, after cooling, obtain the titanium-based type
Steady photovoltaic electrodes；
Preferably, from 0 DEG C to 198-202 DEG C heating 30-35min, 50-70 minutes are incubated at 198-202 DEG C, then in 40min
500-550 DEG C is inside warming up to, and 50-70 minutes are incubated at 500-550 DEG C, more than 8-9 times is repeated and operates, after cooling, obtain
The steady photovoltaic electrodes of titanium-based type.
4. the preparation method of the steady photovoltaic electrodes of titanium-based type according to claim 1, it is characterised in that in step (1), institute
The preparation method of Ag/AgCl photocatalytic nanometer particles is stated, specifically includes following steps：By AgNO3Add ammoniacal liquor in, then spend from
Sub- water dilutes constant volume, adds concentrated hydrochloric acid after stirring evenly, is stirred vigorously, and forms unit for uniform suspension, the suspension is mixed with absolute ethyl alcohol
Close, be aerated and add light irradiation simultaneously, after centrifugation, using deionized water rinsing, be dried at room temperature for constant weight, be somebody's turn to do
Ag/AgCl photocatalytic nanometer particles；
Wherein, the AgNO3Mass ratio with the ammoniacal liquor is 1:(9-10), preferably 1:9.97；The AgNO3With it is described dense
The mass ratio of hydrochloric acid is 1：(8.4-8.6), preferably 1:8.42；
Preferably, the time of the stirring is 22-26h.
5. the preparation method of the steady photovoltaic electrodes of titanium-based type according to claim 4, it is characterised in that the absolute ethyl alcohol
Volume is (0.9-1.0) with the volume ratio after the dilution constant volume with deionized water：1.
6. the preparation method of the steady photovoltaic electrodes of titanium-based type according to claim 4, it is characterised in that described plus light irradiation
Time is 50-70 minutes.
7. the preparation method of the steady photovoltaic electrodes of titanium-based type according to claim 1, it is characterised in that in step (2),
It is described be placed in baking oven dry during, the temperature of the drying is 100-120 DEG C, and the time of the preferable drying is
20-30min。
8. the preparation method of the steady photovoltaic electrodes of titanium-based type according to claim 1, it is characterised in that in step (2), institute
State SnO2The preparation method of the steady electrode of-Sb/Ti types, specifically includes following steps：
On the titanium electrode of etched processing, the n-butanol presoma of stannic chloride pentahydrate and antimony trichloride, forerunner are brushed
The mol ratio of tin and antimony is 9 in body:1, dried after brushing, 10-15min is then calcined at 540-560 DEG C, repetition is dried and forged
Burn two to operate 8-9 times, the SnO is obtained after natural cooling2The steady electrode of-Sb/Ti types；
Preferably, the calcining is operated using Muffle furnace；
Preferably, the temperature of the drying is 100-120 DEG C, and the time of drying is 20-25min；It is furthermore preferred that the drying is adopted
Operated with air dry oven.
9. the steady light of titanium-based type prepared by the preparation method of the steady photovoltaic electrodes of titanium-based type according to claim any one of 1-8
Electrode.
10. the titanium-based type prepared by the preparation method of the steady photovoltaic electrodes of titanium-based type according to claim any one of 1-8 is steady
Application of the photovoltaic electrodes in photoelectrocatalysis organic wastewater.
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