CN104047019A - Artificial antibody type titanium dioxide (TiO2)/ boron-doped diamond (BDD) membrane electrode and preparation method thereof - Google Patents
Artificial antibody type titanium dioxide (TiO2)/ boron-doped diamond (BDD) membrane electrode and preparation method thereof Download PDFInfo
- Publication number
- CN104047019A CN104047019A CN201310077139.1A CN201310077139A CN104047019A CN 104047019 A CN104047019 A CN 104047019A CN 201310077139 A CN201310077139 A CN 201310077139A CN 104047019 A CN104047019 A CN 104047019A
- Authority
- CN
- China
- Prior art keywords
- bdd
- electrode
- boron
- doped diamond
- titanium dioxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The invention relates to an artificial antibody type titanium dioxide (TiO2)/ boron-doped diamond (BDD) membrane electrode and a preparation method thereof, the electrode is in p-n heterostructure, the electrode uses boron-doped diamond (BDD) as a substrate, uniform dense fusiform TiO2 particles are on the surface of the BDD, the particle size of the TiO2 particles is 50-100nm, a modification layer with a thickness of 5 to 10 mum is formed by the densely covered TiO2 particles; the preparation method of the artificial antibody type titanium dioxide (TiO2)/ boron-doped diamond (BDD) membrane electrode is as follows: using of the boron-doped diamond as the substrate, low temperature liquid phase deposition of TiO2 with a target pollutant molecular imprinting on the surface of the substrate, and removal of target pollutant molecules. Compared with the prior art, the artificial antibody type titanium dioxide (TiO2)/ boron-doped diamond (BDD) membrane electrode prepared by the method both has the p-n heterostructure and target pollutant molecular recognition ability, has excellent photoelectrocatalytic integrative performance and high selectivity degradation ability, has the advantages of simple preparation process, can be effectively used for removal of organic pollutants with low concentration, low tendency to biochemistry and high toxicity, and has extensive economic and social benefits.
Description
Technical field
The invention belongs to materials chemistry, Environmental electrochemistry and Pollutant Control Technology field, relate to a kind of electrode and preparation method thereof, especially relate to a kind of artificial anitibody type titanium dioxide/boron-doped diamond film electrode and preparation method thereof.
Background technology
In recent years, the mankind, in daily productive life, are discharged into thousands of organic compound material in water body environment, and the environment that wherein most chemical substance can be depended on for existence to people causes serious harm.According to its toxicity, carinogenicity, biological accumulation; bio-degradable etc.; have a variety of chemical substances by Environmental Protection Agency (USEPA), to be classified as priority pollutants list, wherein, 90% belongs to high toxicity organic pollutant (HTOPs).
In order to remove these high toxicity organic pollutants in water body, various standards are issued use, comprise chemical degradation (chemical oxidation, electrochemical method and photochemical method), oxidation degradation, physical adsorption, precipitation and filtration etc.But, for current complicated and diversified pollutent waste water system, high toxicity not the pollutent of bio-degradable often concentration is lower, and the Pollutant levels of the hypotoxicity bio-degradable coexisting with it are higher, a method of comparatively effectively processing this type of Wastewater Pollutant, for first the organism of high toxicity lower concentration is carried out to photochemical catalytic oxidation, then utilizes biodegradable method to process it.Therefore the selectivity that, how to realize photoelectrocatalysioxidization oxidization process becomes problem a few days ago in the urgent need to address.
Titanium dioxide (TiO
2) as a kind of N-shaped semiconductor material, thering is low toxicity, catalytic capability is strong, good stability and the advantage such as cheap, a kind of good catalyzer of Chang Zuowei is for the Treatment by Photocatalysis Oxidation of water pollutant.TiO
2oxidation mechanism be that in water body, it can produce the hydroxyl radical free radical (OH) with strong oxidation capacity under the exciting of UV-light, the redox reaction of then-OH and pollutent generation non-selectivity lower than its redox potential.Wherein ,-OH has high normal potential (E (OH/H
2o) be=2.80V vs.NHE), the oxidizing substance that a kind of oxidation capacity is only second to fluorine.Yet, if by TiO
2be directly used in the pre-treatment of above-mentioned waste water, a significant drawbacks is exactly that the catalyzed degradation of highly toxic organic pollutant is not had to selectivity.Therefore, improve TiO
2light-catalysed selectivity has become study hotspot and the new difficult problem in environmental catalysis field.
Selectivity mentioned above does not refer to control and the realization to specific response path and reaction product in photochemical catalysis that forefathers report, but to the preferential identification of a certain or several similar compounds in mixed system and selective oxidation degraded.Realize TiO
2the selectivity of photocatalyst has a variety of methods, and for example, by controlling catalyst surface electric charge or different substances rate of mass transfer, the molecular sieve shape selective catalysis of amorphous ti silica photocatalyst, at TiO
2surface graft has the special organic macromolecule of recognition reaction or modifies the macromolecule membrane that one deck has pre-identification function target molecule.But aforesaid method exists some defects, such as the poor stability that, catalysis is selected, can reduce TiO after modifying other material
2light utilization efficiency, and TiO
2can be to modifying organism Oxidative demage in the time of catalyzed degradation.
Molecular imprinting is by using template molecule to obtain a kind of effective ways of specific molecular recognition site in stromal surface.Due to it, there is the features such as special subscription, selectivity and identity, be often used to separation and purification, useful for drug delivery, the preparation of sensor and simulation artificial enzyme catalyzed reaction.Molecular imprinting is applied to TiO
2during photocatalyst synthetic, in catalyzer building-up process, template molecule is directly added, then adopt the methods such as washing, calcining to remove template molecule, at catalyst surface, leave a large amount of recognition sites.Yet the processing that selective photocatalysis will be applied to actual waste water still faces many challenges and difficulty, as the later separation of fine catalyst reclaims, recycle difficulty, because the rapid compound quantum yield that makes in light induced electron and hole is on the low side.Therefore, need to explore effective means and solve these problems.
By TiO
2particle is immobilized on a p-type semiconductor base, not only can make its recycle, and because the depletion layer at n/P interface forms built in field, this electric field is conducive to the separation of photo-generated carrier, thereby greatly improves life-span and the quantum yield of current carrier.In recent years, along with the development of chemical vapour deposition technique, boron doped conductive diamond (BDD) membrane electrode that the silicon single crystal of take is substrate is widely studied and applied.BDD is a kind of p-type semiconductor material of novelty, and its band gap width can carry out Effective Regulation by the doping of boron.Studies have shown that in a large number between N-shaped semi-conductor and p-type BDD, constructing p-n heterojunction can significantly improve the photocatalysis efficiency of organic pollutant and oxidation capacity.
Therefore, by p-type BDD substrate, use, to TiO
2carry out modification, by applying and p-n heterojunction structure raising quantum yield of bias voltage, improve TiO
2photo-catalysis capability, realize optoelectronic integration performance.Introduce molecular imprinting simultaneously, finally obtain a kind of novel electrode with highly selective degradation capability, for research and the application of the selective light electrocatalytic oxidation method of the difficult biochemical high toxicity organic pollutant of lower concentration, have great significance.
Summary of the invention
Object of the present invention is exactly to provide a kind of artificial anitibody type titanium dioxide/boron-doped diamond film electrode that is applicable to selective light Electrocatalysis Degradation Organic Pollutants in Wastewater and preparation method thereof in order to overcome the defect of above-mentioned prior art existence.
Object of the present invention can be achieved through the following technical solutions:
Artificial anitibody type titanium dioxide/boron-doped diamond film electrode, this electrode is p-n heterojunction structure, it is substrate that described electrode be take boron-doped diamond (BDD), even intensive fusoid TiO on BDD surface
2particle, TiO
2the particle diameter of particle is 50～100nm, TiO
2the densely covered formation of particle thickness is the decorative layer of 5～10 μ m, and described electrode is the three-dimensional porous space structure of surface irregularity and porous.
A kind of preparation method of artificial anitibody type titanium dioxide/boron-doped diamond film electrode, take boron-doped diamond as substrate, on substrate surface, low temperature liquid phase deposition has the titanium dioxide of target contaminant molecule (template molecule) trace, remove again target contaminant molecule, obtain artificial anitibody type titanium dioxide/boron-doped diamond film electrode.
The method comprises the following steps:
(1) BDD is carried out to scrubbing and oxide treatment, obtain the BDD membrane electrode that surface has hydrophilic hydroxyl radical free radical terminal;
(2) preparation is containing TiOSO
4, H
2sO
4, concentrated hydrochloric acid and target contaminant solution;
(3) BDD membrane electrode step (1) being obtained is put into the solution of step (2) configuration, under circulating water, carries out back flow reaction, obtains heterojunction TiO
2/ BDD electrode ((MI, n-P)-TiO
2/ BDD electrode);
(4) to heterojunction TiO
2/ BDD electrode washs, calcines removes target contaminant molecule, obtains artificial anitibody type titanium dioxide/boron-doped diamond film electrode, and this electrode is (MI, n-P)-TiO2/BDD electrode with highly selective photoelectrochemical degradation ability.
Wherein, what step (1) was described carries out scrubbing and oxide treatment to BDD, obtaining the concrete grammar that surface has the BDD membrane electrode of hydrophilic hydroxyl radical free radical terminal is: BDD is immersed and in chloroazotic acid, boils 10～30min, remove surperficial greasy filth and inorganic spot completely, then BDD is immersed in to 1～3M H
2sO
4bias voltage anodic oxidation treatment 10～30min of in electrolytic solution, apply+2～+ 5V, then use respectively ethanol and pure water ultrasonic cleaning, obtain the BDD membrane electrode that surface has hydrophilic hydroxyl radical free radical terminal.
The described preparation of step (2) contains TiOSO
4, H
2sO
4, concentrated hydrochloric acid and target contaminant the concrete grammar of solution be: first preparation is containing 0.01～0.05M TiOSO
4with 1～6M H
2sO
4precursor solution, then in precursor solution, add concentrated hydrochloric acid and target contaminant, at room temperature vigorous stirring is dissolved it completely, finally, with ammoniacal liquor, the pH of mixing solutions is adjusted to 1～2, wherein, the proportionlity of precursor solution and concentrated hydrochloric acid and target contaminant is (20～50mL): (5～10mL): (5～20mg).
The temperature of the back flow reaction that step (3) is described is 60～100 ℃, and the time of back flow reaction is 12～48h.
Step (4) described to heterojunction TiO
2/ BDD electrode washs, calcines that to remove the concrete grammar of target contaminant molecule as follows:
By heterojunction TiO
2deionized water rinsing three times of/BDD electrode, dry naturally, then in the tube furnace of oxygen atmosphere protection, with 1～5 ℃ of min
-1speed be warming up to 300～600 ℃, keep 1～5h, then with 1～5 ℃ of min
-1speed be down to room temperature.
Described target contaminant is a kind of in dihydroxyphenyl propane (BPA) or beta naphthal or both mixtures.Although target contaminant is a kind of in dihydroxyphenyl propane or beta naphthal or both mixtures in the present invention, target contaminant can not represent complicated actual waste water completely, but this research provides a kind of new approaches and novel method for the design and assembly of senior photoelectric integral formed material and the processing of waste water.
Artificial anitibody type titanium dioxide/boron-doped diamond film electrode of the present invention is used for photoelectrocatalysioxidization oxidization degraded simulated wastewater: electrode prepared by the present invention of take is anode, and Ti plate is that electrode area is 4cm to electrode
2, electrode distance keeps 1cm.Selecting power is that the high voltage mercury lamp (predominant wavelength 365nm) of 300W is ultraviolet source, and yield of radiation is 15mW cm
-2.Select 40mg L
-1(0.17mM) BPA and 100mg L
-1(0.69mM) 2-NP (beta naphthal), 0.1M Na
2sO
4for the mixing solutions of supporting electrolyte is as degraded simulated wastewater, reaction volume is 100mL.
Due to the introducing of p-type semiconductor base (BDD), artificial anitibody type titanium dioxide/boron-doped diamond film electrode of the present invention is overcoming TiO
2when powder is difficult to reclaim separation and a recycle difficult problem in actual applications, the existence of p-n heterojunction has improved life-span and the quantum yield of photo-generated carrier greatly, has significantly improved photocatalysis efficiency and the oxidation capacity of electrode for high toxicity organic pollutant.By adopting molecular imprinting, electrode of the present invention has excellent PhotoelectrocatalytiPerformance Performance and highly selective degradation capability, is applicable to preferential identification and the selective oxidation degraded of the difficult biochemical high toxicity pollutent of lower concentration in mixed system.
The present invention utilizes molecular imprinting to construct the TiO with molecular imprinting
2/ BDD combined electrode obtains spindle shape TiO on BDD matrix
2the decorative layer of the even intensive growth of particle, the electrode of acquisition can not only show excellent PhotoelectrocatalytiPerformance Performance, and has the highly selective degradation capability to target contaminant molecule.
Compared with prior art, the present invention has the following advantages and beneficial effect:
1, with the TiO of common two dimensional structure
2film is compared, by spindle shape TiO
2the electrode surface of the three-dimensional porous space structure of particle assembling has higher adsorptive power and more active site.
2, trace building-up process can be TiO
2surface provides the target contaminant molecular recognition site of mass efficient, and TiO
2as a kind of solid stable inorganic matrix material, can keep more accurately, more lasting recognition capability, this has conclusive effect to its photoelectrocatalysis selectivity processing target pollutent.
3, constructing of p-n heterojunction suppressed the compound of photo-generated carrier effectively, thereby improved its photoelectrocatalysis ability.
While 4, BDD being carried out to scrubbing and oxide treatment, impressed voltage plays dredging effect to the transmission of electronics equally.
5, with without (trace, the TiO of p-n heterojunction structure
2)/FTO compares, and this electrode has more excellent PhotoelectrocatalytiPerformance Performance; With the TiO without trace
2/ BDD electrode is compared, and this electrode has high degradation selectivity ability.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the artificial anitibody type titanium dioxide/boron-doped diamond film electrode of embodiment 1 preparation;
Fig. 2 is the I-V performance diagram of heterojunction of the artificial anitibody type titanium dioxide/boron-doped diamond film electrode of embodiment 1 preparation;
Fig. 3 is dihydroxyphenyl propane clearance schematic diagram over time in the artificial anitibody type titanium dioxide/boron-doped diamond film electrode of embodiment 1 preparation and the photoelectrocatalysis process of comparison electrode in the simulated wastewater containing dihydroxyphenyl propane and beta naphthal;
Fig. 4 is beta naphthal clearance schematic diagram over time in the artificial anitibody type titanium dioxide/boron-doped diamond film electrode of embodiment 1 preparation and the photoelectrocatalysis process of comparison electrode in the simulated wastewater containing dihydroxyphenyl propane and beta naphthal.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1
BDD is immersed in chloroazotic acid and boils 10min, remove surperficial greasy filth and inorganic spot completely, follow it at 2M1M H
2sO
4the bias voltage anodic oxidation treatment 10min of in electrolytic solution, apply+3V, with the hydrophilic BDD surface of obtain-OH terminal, finally uses respectively ethanol and pure water ultrasonic cleaning.Preparation 25mL is containing 0.03M TiOSO
4with 3M H
2sO
4solution, then add 6mL concentrated hydrochloric acid and 10mg target contaminant (dihydroxyphenyl propane), at room temperature vigorous stirring 6h, dissolves it completely, last, with ammoniacal liquor, the pH of mixing solutions is adjusted to 1.3, obtains precursor solution.The BDD anticipating (10 * 45mm) electrode is put into the round-bottomed flask of 100mL, the precursor solution of preparation is poured into, solution soaked BDD electrode, 65 ℃ of back flow reaction 24h under circulating water.Taking-up has (MI, the n-P)-TiO of target contaminant trace
2deionized water rinsing three times of/BDD electrode, dry naturally.In order to remove target contaminant template, in the tube furnace of oxygen atmosphere protection, with 2 ℃ of min
-1speed be warming up to 400 ℃, keep 3h, then equally with 2 ℃ of min
-1speed be down to room temperature.Prepare artificial anitibody type titanium dioxide/boron-doped diamond film electrode, this electrode is (MI, n-P)-TiO2/BDD electrode with highly selective photoelectrochemical degradation ability.
The surface topography of artificial anitibody type titanium dioxide/boron-doped diamond film electrode prepared by the present embodiment characterizes by field emission scanning electron microscope (SEM), as shown in Figure 1, can find out fusoid TiO
2particle is the intensive BDD surface that is grown in evenly, and BDD surface is completely covered, the coarse and porous of electrode surface.TiO
2particle diameter is the about 80nm of long axis direction, the about 40nm of short-axis direction, decorative layer thickness 5 μ m.
On the manual probe station of micro-operation of Keithley4200 semiconductor parametric tester, under room temperature in air atmosphere ,-3V applies under voltage to+3V, records the current voltage characteristic that the present embodiment makes electrode, as shown in Figure 2, the illustration in Fig. 2 is the curve that BDD film is corresponding.As we can clearly see from the figure, the I-V curve of electrode is classical skew curve, shows p-n junction rectification characteristic, and TiO is described
2layer and BDD interface formation p-n heterojunction structure.
Embodiment 2
BDD is immersed in chloroazotic acid and boils 30min, remove surperficial greasy filth and inorganic spot completely, follow it at 3M H
2sO
4the bias voltage anodic oxidation treatment 20min of in electrolytic solution, apply+3.5V, with the hydrophilic BDD surface of obtain-OH terminal, finally uses respectively ethanol and pure water ultrasonic cleaning.Preparation 45mL is containing 0.05M TiOSO
4with 5M H
2sO
4solution, then add 8mL concentrated hydrochloric acid and 20mg target contaminant (dihydroxyphenyl propane), at room temperature vigorous stirring 10h, dissolves it completely, last, with ammoniacal liquor, the pH of mixing solutions is adjusted to 1.5, configuration obtains precursor solution.The BDD anticipating (10 * 45mm) electrode is put into the round-bottomed flask of 100mL, the precursor solution of preparation is poured into, solution soaked BDD electrode, 90 ℃ of back flow reaction 48h under circulating water.Taking-up has (MI, the n-P)-TiO of target contaminant trace
2deionized water rinsing three times of/BDD electrode, dry naturally.In order to remove target contaminant template, in the tube furnace of oxygen atmosphere protection, with 5 ℃ of min
-1speed be warming up to 500 ℃, keep 5h, then equally with 5 ℃ of min
-1speed be down to room temperature, prepare artificial anitibody type titanium dioxide/boron-doped diamond film electrode, this electrode is (MI, n-P)-TiO2/BDD electrode with highly selective photoelectrochemical degradation ability.
Embodiment 3
Adopt (MI, the n-P)-TiO preparing in embodiment 1
2the TiO of/BDD electrode and non-trace
2/ BDD electrode photo electrocatalysis oxidative degradation simulated wastewater.
Photoelectric catalysis degrading carries out in the reactor of half round post list pond, the additional a set of cups with recirculated water, and keeping temperature of reaction system is room temperature, uses magneton constantly to stir mass transfer enhancement in degraded.The electrode preparing in embodiment 1 of take is anode, and Ti plate is that electrode area is 4cm to electrode
2, electrode distance keeps 1cm.Selecting power is that the high voltage mercury lamp (predominant wavelength 365nm) of 300W is ultraviolet source, and yield of radiation is 15mW cm
-2.Select 20mgL
-1(0.088mM) BPA and 50mg L
-1(0.347mM) 2-NP (beta naphthal), 0.1M Na
2sO
4for the mixing solutions of supporting electrolyte is as degraded simulated wastewater, reaction volume is 100ml, proceeds to different moment samplings analyze in photoelectrocatalysioxidization oxidization DeR.The concentration of measuring pollutent in degradation process with HPLC over time.
Degradation results is shown in shown in Fig. 3 and Fig. 4, and in figure, a represents (MI, n-P)-TiO
2the TiO of/BDD or non-trace
2the equilibrium adsorption test process of/BDD, b represents the TiO of trace
2the TiO of/FTO electrode or non-trace
2the equilibrium adsorption test process of/FTO electrode, a ' represents (MI, n-P)-TiO
2in the photoelectrocatalysis process of/BDD electrode in the simulated wastewater containing dihydroxyphenyl propane and beta naphthal dihydroxyphenyl propane or beta naphthal clearance over time, a " represent the TiO of non-trace
2in the photoelectrocatalysis process of/BDD electrode in the simulated wastewater containing dihydroxyphenyl propane and beta naphthal, dihydroxyphenyl propane or beta naphthal clearance are over time; B ' represents the TiO of trace
2in the photoelectrocatalysis process of/FTO electrode in the simulated wastewater containing dihydroxyphenyl propane and beta naphthal, dihydroxyphenyl propane or beta naphthal clearance are over time; B " represent the TiO of non-trace
2in the photoelectrocatalysis process of/FTO electrode in the simulated wastewater containing dihydroxyphenyl propane and beta naphthal, dihydroxyphenyl propane or beta naphthal clearance are over time; Wherein, FTO refers to the SnO of doped with fluorine
2transparent conducting glass.Degradation results shows, after 2h, target contaminant BPA is at the TiO of non-trace
2clearance on/BDD is only 61%, the clearance 97% of the electrode making far below embodiment 1.And for chaff interference 2-NP, at the TiO of non-trace
2clearance on/BDD and trace electrode (MI, n-P)-TiO
2clearance on/BDD is respectively 61% and 53%, compares and take photo cathode material that FTO is substrate owing to not forming p-n heterojunction structure, and photoelectric catalysis degrading efficiency and selectivity are all lower than take the photo cathode material that BDD is substrate.Trace electrode (MI, n-P)-TiO has been described
2/ BDD has high selective light Electrocatalysis Degradation ability for target contaminant.
Embodiment 4
Adopt (MI, the n-P)-TiO preparing in embodiment 2
2the TiO of/BDD electrode and non-trace
2/ BDD electrode photo electrocatalysis oxidative degradation simulated wastewater.
Photoelectric catalysis degrading carries out in the reactor of half round post list pond, the additional a set of cups with recirculated water, and keeping temperature of reaction system is room temperature, uses magneton constantly to stir mass transfer enhancement in degraded.The electrode of preparing of take is anode, and Ti plate is that electrode area is 4cm to electrode
2, electrode distance keeps 1cm.Selecting power is that the high voltage mercury lamp (predominant wavelength 365nm) of 300W is ultraviolet source, and yield of radiation is 15mW cm
-2.Select 40mg L
-1(0.17mM) BPA and 100mg L
-1(0.69mM) 2-NP (beta naphthal), 0.1M Na
2sO
4for the mixing solutions of supporting electrolyte is as degraded simulated wastewater, reaction volume is 100mL, and photoelectrocatalysioxidization oxidization degraded sample in the same time is not analyzed.Over time, after 2h, target contaminant BPA is at the TiO of non-trace for the concentration of measuring primary pollutant with HPLC
2clearance on/BDD is only 47%, far below trace electrode (MI, n-P)-TiO
2the clearance 85% of/BDD.And for chaff interference 2-NP, at the TiO of non-trace
2clearance on/BDD and trace electrode (MI, n-P)-TiO
2clearance on/BDD is respectively 51% and 40%, same, compares and take photo cathode material that FTO is substrate owing to not forming p-n heterojunction structure, and photoelectric catalysis degrading efficiency and selectivity are all lower than take the photo cathode material that BDD is substrate.
Embodiment 5
Artificial anitibody type titanium dioxide/boron-doped diamond film electrode, this electrode is p-n heterojunction structure, it is substrate that electrode be take boron-doped diamond (BDD), even intensive fusoid TiO on BDD surface
2particle, TiO
2the particle diameter of particle is 50～100nm, TiO
2the densely covered formation of particle thickness is the decorative layer of 5 μ m, and electrode is the three-dimensional porous space structure of surface irregularity and porous.
A kind of preparation method of artificial anitibody type titanium dioxide/boron-doped diamond film electrode, take boron-doped diamond as substrate, on substrate surface, low temperature liquid phase deposition has the titanium dioxide of target contaminant molecule (template molecule) trace, remove again target contaminant molecule, obtain artificial anitibody type titanium dioxide/boron-doped diamond film electrode.
The method comprises the following steps:
(1) BDD is carried out to scrubbing and oxide treatment, obtains the BDD membrane electrode that surface has hydrophilic hydroxyl radical free radical terminal:
BDD is immersed in chloroazotic acid and boils 10min, remove surperficial greasy filth and inorganic spot completely, then BDD is immersed in to 1M H
2sO
4the bias voltage anodic oxidation treatment 10min of in electrolytic solution, apply+2V, then use respectively ethanol and pure water ultrasonic cleaning, obtain the BDD membrane electrode that surface has hydrophilic hydroxyl radical free radical terminal;
(2) preparation is containing TiOSO
4, H
2sO
4, concentrated hydrochloric acid and target contaminant solution:
First prepare 20mL containing 0.01M TiOSO
4with 1M H
2sO
4solution, then add 5mL concentrated hydrochloric acid and 5mg target contaminant, at room temperature vigorous stirring is dissolved it completely, last, with ammoniacal liquor, the pH of mixing solutions is adjusted to 1;
(3) BDD membrane electrode step (1) being obtained is put into the solution of step (2) configuration, under circulating water, carries out back flow reaction, and the temperature of back flow reaction is 60 ℃, and the time of back flow reaction is 12h, obtains heterojunction TiO
2/ BDD electrode ((MI, n-P)-TiO
2/ BDD electrode);
(4) to heterojunction TiO
2/ BDD electrode washs, calcines removes target contaminant molecule, by heterojunction TiO
2deionized water rinsing three times of/BDD electrode, dry naturally, then in the tube furnace of oxygen atmosphere protection, with 1 ℃ of min
-1speed be warming up to 300 ℃, keep 5h, then with 1 ℃ of min
-1speed be down to room temperature, obtain artificial anitibody type titanium dioxide/boron-doped diamond film electrode, this electrode is (MI, n-P)-TiO2/BDD electrode with highly selective photoelectrochemical degradation ability.
Embodiment 6
Artificial anitibody type titanium dioxide/boron-doped diamond film electrode, this electrode is p-n heterojunction structure, it is substrate that electrode be take boron-doped diamond (BDD), even intensive fusoid TiO on BDD surface
2particle, TiO
2the particle diameter of particle is 50～100nm, TiO
2the densely covered formation of particle thickness is the decorative layer of 8 μ m, and electrode is the three-dimensional porous space structure of surface irregularity and porous.
A kind of preparation method of artificial anitibody type titanium dioxide/boron-doped diamond film electrode, take boron-doped diamond as substrate, on substrate surface, low temperature liquid phase deposition has the titanium dioxide of target contaminant molecule (template molecule) trace, remove again target contaminant molecule, obtain artificial anitibody type titanium dioxide/boron-doped diamond film electrode.
The method comprises the following steps:
(1) BDD is carried out to scrubbing and oxide treatment, obtains the BDD membrane electrode that surface has hydrophilic hydroxyl radical free radical terminal:
BDD is immersed in chloroazotic acid and boils 20min, remove surperficial greasy filth and inorganic spot completely, then BDD is immersed in to 2M H
2sO
4the bias voltage anodic oxidation treatment 20min of in electrolytic solution, apply+4V, then use respectively ethanol and pure water ultrasonic cleaning, obtain the BDD membrane electrode that surface has hydrophilic hydroxyl radical free radical terminal;
(2) preparation is containing TiOSO
4, H
2sO
4, concentrated hydrochloric acid and target contaminant solution:
First prepare 30mL containing 0.03M TiOSO
4with 3M H
2sO
4solution, then add 8mL concentrated hydrochloric acid and 10mg target contaminant, at room temperature vigorous stirring is dissolved it completely, last, with ammoniacal liquor, the pH of mixing solutions is adjusted to 1.5;
(3) BDD membrane electrode step (1) being obtained is put into the solution of step (2) configuration, under circulating water, carries out back flow reaction, and the temperature of back flow reaction is 80 ℃, and the time of back flow reaction is 24h, obtains heterojunction TiO
2/ BDD electrode ((MI, n-P)-TiO
2/ BDD electrode);
(4) to heterojunction TiO
2/ BDD electrode washs, calcines removes target contaminant molecule, by heterojunction TiO
2deionized water rinsing three times of/BDD electrode, dry naturally, then in the tube furnace of oxygen atmosphere protection, with 2 ℃ of min
-1speed be warming up to 400 ℃, keep 3h, then with 2 ℃ of min
-1speed be down to room temperature, obtain artificial anitibody type titanium dioxide/boron-doped diamond film electrode, this electrode is (MI, n-P)-TiO2/BDD electrode with highly selective photoelectrochemical degradation ability.
Embodiment 7
Artificial anitibody type titanium dioxide/boron-doped diamond film electrode, this electrode is p-n heterojunction structure, it is substrate that electrode be take boron-doped diamond (BDD), even intensive fusoid TiO on BDD surface
2particle, TiO
2the particle diameter of particle is 50～100nm, TiO
2the densely covered formation of particle thickness is the decorative layer of 10 μ m, and electrode is the three-dimensional porous space structure of surface irregularity and porous.
A kind of preparation method of artificial anitibody type titanium dioxide/boron-doped diamond film electrode, take boron-doped diamond as substrate, on substrate surface, low temperature liquid phase deposition has the titanium dioxide of target contaminant molecule (template molecule) trace, remove again target contaminant molecule, obtain artificial anitibody type titanium dioxide/boron-doped diamond film electrode.
The method comprises the following steps:
(1) BDD is carried out to scrubbing and oxide treatment, obtains the BDD membrane electrode that surface has hydrophilic hydroxyl radical free radical terminal:
BDD is immersed in chloroazotic acid and boils 30min, remove surperficial greasy filth and inorganic spot completely, then BDD is immersed in to 3M H
2sO
4the bias voltage anodic oxidation treatment 30min of in electrolytic solution, apply+5V, then use respectively ethanol and pure water ultrasonic cleaning, obtain the BDD membrane electrode that surface has hydrophilic hydroxyl radical free radical terminal;
(2) preparation is containing TiOSO
4, H
2sO
4, concentrated hydrochloric acid and target contaminant solution:
First prepare 50mL containing 0.05M TiOSO
4with 6M H
2sO
4solution, then add 10mL concentrated hydrochloric acid and 20mg target contaminant, at room temperature vigorous stirring is dissolved it completely, last, with ammoniacal liquor, the pH of mixing solutions is adjusted to 2;
(3) BDD membrane electrode step (1) being obtained is put into the solution of step (2) configuration, under circulating water, carries out back flow reaction, and the temperature of back flow reaction is 100 ℃, and the time of back flow reaction is 48h, obtains heterojunction TiO
2/ BDD electrode ((MI, n-P)-TiO
2/ BDD electrode);
(4) to heterojunction TiO
2/ BDD electrode washs, calcines removes target contaminant molecule, by heterojunction TiO
2deionized water rinsing three times of/BDD electrode, dry naturally, then in the tube furnace of oxygen atmosphere protection, with 5 ℃ of min
-1speed be warming up to 600 ℃, keep 1h, then with 5 ℃ of min
-1speed be down to room temperature, obtain artificial anitibody type titanium dioxide/boron-doped diamond film electrode, this electrode is (MI, n-P)-TiO2/BDD electrode with highly selective photoelectrochemical degradation ability.
Above-described embodiment proves: on BDD matrix, adopt low temperature liquid phase deposition method, by the TiO with molecular imprinting
2deposition, can obtain the TiO with the integrated performance of high photoelectrocatalysis
2/ BDD combined electrode, and the degradation selectivity ability of electrode improves greatly than the electrode of not constructing molecular imprinting.This electrode can be used for the photoelectrocatalysis degradation selectivity of the difficult biochemical high toxicity organic waste water of lower concentration to be processed.
The above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.Person skilled in the art obviously can easily make various modifications to these embodiment, and General Principle described herein is applied in other embodiment and needn't passes through performing creative labour.Therefore, the invention is not restricted to the embodiment here, those skilled in the art are according to announcement of the present invention, and the improvement of making for the present invention and modification all should be within protection scope of the present invention.
Claims (8)
1. artificial anitibody type titanium dioxide/boron-doped diamond film electrode, is characterized in that, this electrode is p-n heterojunction structure, and it is substrate that described electrode be take boron-doped diamond (BDD), even intensive fusoid TiO on BDD surface
2particle, TiO
2the particle diameter of particle is 50～100nm, TiO
2the densely covered formation of particle thickness is the decorative layer of 5～101 μ m.
2. the preparation method of an artificial anitibody type titanium dioxide/boron-doped diamond film electrode as claimed in claim 1, it is characterized in that, take boron-doped diamond as substrate, on substrate surface, low temperature liquid phase deposition has the titanium dioxide of target contaminant molecular imprinting, remove again target contaminant molecule, obtain artificial anitibody type titanium dioxide/boron-doped diamond film electrode.
3. the preparation method of a kind of artificial anitibody type titanium dioxide/boron-doped diamond film electrode according to claim 2, is characterized in that, the method comprises the following steps:
(1) BDD is carried out to scrubbing and oxide treatment, obtain the BDD membrane electrode that surface has hydrophilic hydroxyl radical free radical terminal;
(2) preparation is containing TiOSO
4, H
2sO
4, concentrated hydrochloric acid and target contaminant solution;
(3) BDD membrane electrode step (1) being obtained is put into the solution of step (2) configuration, under circulating water, carries out back flow reaction, obtains heterojunction TiO
2/ BDD electrode;
(4) to heterojunction TiO
2/ BDD electrode washs, calcines removes target contaminant molecule, obtains artificial anitibody type titanium dioxide/boron-doped diamond film electrode.
4. the preparation method of a kind of artificial anitibody type titanium dioxide/boron-doped diamond film electrode according to claim 3, it is characterized in that, what step (1) was described carries out scrubbing and oxide treatment to BDD, obtains the surperficial concrete grammar with the BDD membrane electrode of hydrophilic hydroxyl radical free radical terminal to be:
BDD is immersed in chloroazotic acid and boils 10～30min, remove surperficial greasy filth and inorganic spot completely, then BDD is immersed in to 1～3M H
2sO
4bias voltage anodic oxidation treatment 10～30min of in electrolytic solution, apply+2～+ 5V, then use respectively ethanol and pure water ultrasonic cleaning, obtain the BDD membrane electrode that surface has hydrophilic hydroxyl radical free radical terminal.
5. the preparation method of a kind of artificial anitibody type titanium dioxide/boron-doped diamond film electrode according to claim 3, is characterized in that, the described preparation of step (2) contains TiOSO
4, H
2sO
4, concentrated hydrochloric acid and target contaminant the concrete grammar of solution be:
First preparation is containing 0.01～0.05M TiOSO
4with 1～6M H
2sO
4precursor solution, then in precursor solution, add concentrated hydrochloric acid and target contaminant, at room temperature vigorous stirring is dissolved it completely, finally, with ammoniacal liquor, the pH of mixing solutions is adjusted to 1～2, wherein, the proportionlity of precursor solution and concentrated hydrochloric acid and target contaminant is (20～50mL): (5～10mL): (5～20mg).
6. the preparation method of a kind of artificial anitibody type titanium dioxide/boron-doped diamond film electrode according to claim 3, is characterized in that, the temperature of the back flow reaction that step (3) is described is 60～100 ℃, and the time of back flow reaction is 12～48h.
7. the preparation method of a kind of artificial anitibody type titanium dioxide/boron-doped diamond film electrode according to claim 3, is characterized in that, step (4) described to heterojunction TiO
2/ BDD electrode washs, calcines that to remove the concrete grammar of target contaminant molecule as follows:
By heterojunction TiO
2deionized water rinsing three times of/BDD electrode, dry naturally, then in the tube furnace of oxygen atmosphere protection, with 1～5 ℃ of min
-1speed be warming up to 300～600 ℃, keep 1～5h, then with 1～5 ℃ of min
-1speed be down to room temperature.
8. according to the preparation method of claim 2,3,5 or 7 arbitrary described a kind of artificial anitibody type titanium dioxide/boron-doped diamond film electrodes, it is characterized in that, described target contaminant is a kind of in dihydroxyphenyl propane or beta naphthal or both mixtures.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310077139.1A CN104047019A (en) | 2013-03-11 | 2013-03-11 | Artificial antibody type titanium dioxide (TiO2)/ boron-doped diamond (BDD) membrane electrode and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310077139.1A CN104047019A (en) | 2013-03-11 | 2013-03-11 | Artificial antibody type titanium dioxide (TiO2)/ boron-doped diamond (BDD) membrane electrode and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104047019A true CN104047019A (en) | 2014-09-17 |
Family
ID=51500403
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310077139.1A Pending CN104047019A (en) | 2013-03-11 | 2013-03-11 | Artificial antibody type titanium dioxide (TiO2)/ boron-doped diamond (BDD) membrane electrode and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104047019A (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104944512A (en) * | 2015-06-17 | 2015-09-30 | 张易祥 | Method for effectively degrading algal toxin in water |
| CN105401150A (en) * | 2015-11-09 | 2016-03-16 | 郑州大学 | TiO2 nano-beam/boron-doped diamond film composite photoelectrocatalysis electrode and preparation method and application thereof |
| CN105689012A (en) * | 2015-12-15 | 2016-06-22 | 中国石油大学(华东) | Preparation method of nano diamond solid acid catalyst |
| CN106987861A (en) * | 2017-04-12 | 2017-07-28 | 东华大学 | A kind of method that electrolytic catalysis prepares 2,5 dimethoxy dihydrofuran |
| CN107200383A (en) * | 2017-06-29 | 2017-09-26 | 同济大学 | A kind of method that selective light electrocatalytic oxidation removes Atrazine |
| CN107794549A (en) * | 2017-09-04 | 2018-03-13 | 天津大学 | Preparation method of ethers |
| CN107986401A (en) * | 2017-12-20 | 2018-05-04 | 深圳先进技术研究院 | A kind of boron-doped diamond electrode and preparation method thereof |
| CN108452788A (en) * | 2018-05-09 | 2018-08-28 | 同济大学 | The preparation method and application of interstitial boron doped titanium dioxide photocatalytic material |
| JP2019005709A (en) * | 2017-06-26 | 2019-01-17 | 学校法人東京理科大学 | Purification apparatus, purification method, carbon material manufacturing method and carbon material |
| CN110921786A (en) * | 2019-11-23 | 2020-03-27 | 同济大学 | Photoelectrocatalysis anode material for removing phthalate and treatment method |
| CN111646632A (en) * | 2020-05-11 | 2020-09-11 | 南京岱蒙特科技有限公司 | Green energy-saving photoelectrocatalysis water treatment system and water treatment method thereof |
| US11377373B2 (en) * | 2019-07-10 | 2022-07-05 | Tongji University | Electrochemical membrane module for selectively removing pollutants and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101555050A (en) * | 2008-04-08 | 2009-10-14 | 中国科学院生态环境研究中心 | Method for preparing BDD-TiO2 pole with P-N junction characteristic |
| CN101786026A (en) * | 2010-03-24 | 2010-07-28 | 吉林大学 | n-shaped titanium oxide nanotube/p-shaped diamond heterojunction photocatalytic material and preparation method |
| WO2011100253A2 (en) * | 2010-02-11 | 2011-08-18 | Hach Company | Carbon quantifying apparatus and method |
-
2013
- 2013-03-11 CN CN201310077139.1A patent/CN104047019A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101555050A (en) * | 2008-04-08 | 2009-10-14 | 中国科学院生态环境研究中心 | Method for preparing BDD-TiO2 pole with P-N junction characteristic |
| WO2011100253A2 (en) * | 2010-02-11 | 2011-08-18 | Hach Company | Carbon quantifying apparatus and method |
| WO2011100253A3 (en) * | 2010-02-11 | 2011-12-29 | Hach Company | Carbon quantifying apparatus and method |
| CN101786026A (en) * | 2010-03-24 | 2010-07-28 | 吉林大学 | n-shaped titanium oxide nanotube/p-shaped diamond heterojunction photocatalytic material and preparation method |
Non-Patent Citations (2)
| Title |
|---|
| SHOUNING CHAI: "Selective Photoelectrocatalytic Degradation of Recalcitrant Contaminant Driven by an n‑P Heterojunction Nanoelectrode with Molecular Recognition Ability", 《ENVIRONMENTAL SCIENCE & TECHNOLOGY》 * |
| SHOUNING CHAI: "Selective Photoelectrocatalytic Degradation of Recalcitrant Contaminant Driven by an n‑P Heterojunction Nanoelectrode with Molecular Recognition Ability", 《ENVIRONMENTAL SCIENCE & TECHNOLOGY》, no. 46, 24 August 2012 (2012-08-24), pages 10182 - 10190 * |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104944512A (en) * | 2015-06-17 | 2015-09-30 | 张易祥 | Method for effectively degrading algal toxin in water |
| CN105401150A (en) * | 2015-11-09 | 2016-03-16 | 郑州大学 | TiO2 nano-beam/boron-doped diamond film composite photoelectrocatalysis electrode and preparation method and application thereof |
| CN105401150B (en) * | 2015-11-09 | 2018-01-05 | 郑州大学 | A kind of TiO2Nanometer bundle/boron-doped diamond film composite photoelectric catalysis electrode, preparation method and application |
| CN105689012A (en) * | 2015-12-15 | 2016-06-22 | 中国石油大学(华东) | Preparation method of nano diamond solid acid catalyst |
| CN106987861A (en) * | 2017-04-12 | 2017-07-28 | 东华大学 | A kind of method that electrolytic catalysis prepares 2,5 dimethoxy dihydrofuran |
| CN106987861B (en) * | 2017-04-12 | 2019-02-01 | 东华大学 | A kind of method of electrolytic catalysis preparation 2,5- dimethoxy dihydrofuran |
| JP2019005709A (en) * | 2017-06-26 | 2019-01-17 | 学校法人東京理科大学 | Purification apparatus, purification method, carbon material manufacturing method and carbon material |
| JP7012951B2 (en) | 2017-06-26 | 2022-01-31 | 学校法人東京理科大学 | Purification equipment, purification method, carbon material manufacturing method and carbon material |
| CN107200383A (en) * | 2017-06-29 | 2017-09-26 | 同济大学 | A kind of method that selective light electrocatalytic oxidation removes Atrazine |
| CN107794549B (en) * | 2017-09-04 | 2020-03-31 | 天津大学 | Preparation method of ethers |
| CN107794549A (en) * | 2017-09-04 | 2018-03-13 | 天津大学 | Preparation method of ethers |
| CN107986401A (en) * | 2017-12-20 | 2018-05-04 | 深圳先进技术研究院 | A kind of boron-doped diamond electrode and preparation method thereof |
| CN108452788A (en) * | 2018-05-09 | 2018-08-28 | 同济大学 | The preparation method and application of interstitial boron doped titanium dioxide photocatalytic material |
| US11377373B2 (en) * | 2019-07-10 | 2022-07-05 | Tongji University | Electrochemical membrane module for selectively removing pollutants and preparation method thereof |
| CN110921786A (en) * | 2019-11-23 | 2020-03-27 | 同济大学 | Photoelectrocatalysis anode material for removing phthalate and treatment method |
| CN110921786B (en) * | 2019-11-23 | 2021-11-09 | 同济大学 | Photoelectrocatalysis anode material for removing phthalate and treatment method |
| CN111646632A (en) * | 2020-05-11 | 2020-09-11 | 南京岱蒙特科技有限公司 | Green energy-saving photoelectrocatalysis water treatment system and water treatment method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104047019A (en) | Artificial antibody type titanium dioxide (TiO2)/ boron-doped diamond (BDD) membrane electrode and preparation method thereof | |
| Wang et al. | Visible light photoreduction of CO2 using CdSe/Pt/TiO2 heterostructured catalysts | |
| Liu et al. | Enhanced photocatalysis on TiO2 nanotube arrays modified with molecularly imprinted TiO2 thin film | |
| Liu et al. | Efficient electricity production and simultaneously wastewater treatment via a high-performance photocatalytic fuel cell | |
| Zarei et al. | Fundamentals and some applications of photoelectrocatalysis and effective factors on its efficiency: a review | |
| Guo et al. | High photocatalytic capability of self-assembled nanoporous WO3 with preferential orientation of (002) planes | |
| Wang et al. | Enhancing the photoelectrochemical water oxidation reaction of BiVO4 photoanode by employing carbon spheres as electron reservoirs | |
| Yang et al. | Fabrication of CdSe nanoparticles sensitized long TiO2 nanotube arrays for photocatalytic degradation of anthracene-9-carbonxylic acid under green monochromatic light | |
| Daskalaki et al. | Solar light-responsive Pt/CdS/TiO2 photocatalysts for hydrogen production and simultaneous degradation of inorganic or organic sacrificial agents in wastewater | |
| Primo et al. | Efficient visible-light photocatalytic water splitting by minute amounts of gold supported on nanoparticulate CeO2 obtained by a biopolymer templating method | |
| Chen et al. | Visible-light responsive photocatalytic fuel cell based on WO3/W photoanode and Cu2O/Cu photocathode for simultaneous wastewater treatment and electricity generation | |
| Liu et al. | All inorganic semiconductor nanowire mesh for direct solar water splitting | |
| Ba et al. | New way for CO2 reduction under visible light by a combination of a Cu electrode and semiconductor thin film: Cu2O conduction type and morphology effect | |
| Wang et al. | Fabrication of PbO2 tipped Co3O4 nanowires for efficient photoelectrochemical decolorization of dye (reactive brilliant blue KN-R) wastewater | |
| Nagakawa et al. | Visible-light overall water splitting by CdS/WO3/CdWO4 tricomposite photocatalyst suppressing photocorrosion | |
| CN106498372B (en) | Light deposition prepares Bi/BiVO4The method of composite photoelectric anode material | |
| CN105442012B (en) | A kind of composite nano materials MoS2/TiO2The preparation method and applications of nano-tube array | |
| Ouyang et al. | CdS-sensitized ZnO nanorod arrays coated with TiO 2 layer for visible light photoelectrocatalysis | |
| CN109092319B (en) | WO (WO)3/BiVO4Ternary system composite material of/FeOOH and preparation method and application thereof | |
| Wang et al. | Promoting charge separation and injection by optimizing the interfaces of GaN: ZnO photoanode for efficient solar water oxidation | |
| Fu et al. | Structural-dependent photoactivities of TiO2 nanoribbon for visible-light-induced H2 evolution: the roles of nanocavities and alternate structures | |
| Lu et al. | In situ integration of ReS2/Ni3S2 pn heterostructure for enhanced photoelectrocatalytic performance | |
| Luo et al. | Self-driven photoelectrochemical splitting of H2S for S and H2 recovery and simultaneous electricity generation | |
| Yu et al. | A self-biased fuel cell with TiO2/g-C3N4 anode catalyzed alkaline pollutant degradation with light and without light—What is the degradation mechanism? | |
| Cai et al. | Porous ZnO@ ZnSe nanosheet array for photoelectrochemical reduction of CO2 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20140917 |