CN101905912A - Method for preparing organic pollutant-degrading electrode material - Google Patents
Method for preparing organic pollutant-degrading electrode material Download PDFInfo
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- CN101905912A CN101905912A CN2010102253891A CN201010225389A CN101905912A CN 101905912 A CN101905912 A CN 101905912A CN 2010102253891 A CN2010102253891 A CN 2010102253891A CN 201010225389 A CN201010225389 A CN 201010225389A CN 101905912 A CN101905912 A CN 101905912A
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Abstract
The invention relates to the technical field of electrochemistry and relates to a method for preparing an organic pollutant-degrading electrode material. The prepared electrode material for degrading the organic pollutant CO has a cladding structure in which a titanium matrix, a tantalum interlayer and a diamond film are clad in sequence, wherein the surface of the titanium matrix is clad with the tantalum interlayer which is in closed fit with the matrix; the boron-doped diamond film is deposited on the outside of the tantalum interlayer; the titanium matrix has a purity mass percentage of no less than 99 percent and the thickness of the composite tantalum interlayer is 1 mu m so as to protect the titanium matrix, restrain the growth of titanium carbide (TiC) and prolong the service life of the electrode; and the resisitivity of the boron-doped diamond film is 10<9> to 10<12> omega.cm, and a conductive diamond film electrode is prepared by controlling the doping amount of boron. The method has the advantages that: the process is simple, safe and reliable; the prepared electrode material has high cost performance, a wide potential window and a high degradation effect; the diamond film is not easy to drop in an electrolytic process by settling the tantalum interlayer; and the diamond film electrode has high stability.
Description
Technical field:
The invention belongs to technical field of electrochemistry, relate to a kind of novel electrode material preparation method of degradable organic pollutant, that the electrode materials of this method preparation is applicable to is poisonous, the electrochemical treatment of the high concentration organic contaminant waste water of difficult degradation.
Background technology:
High speed development along with industry, the organic value volume and range of product of chemosynthesis that enters water body sharply increases, cause the characteristics such as organic content height, complicated component, poisonous and harmful, difficult for biological degradation in the waste water, cause the severe contamination of water resources, threatened human existence and development.Present sewage disposal technology mainly comprises physical treatment process, method of chemical treatment and biological treatment, and these treatment processs have superiority separately, also exists the some shortcomings part simultaneously.The organic compound of particularly poisonous for those and difficult for biological degradation, these method major parts are all improper.How handling the difficult for biological degradation organic pollutant has timely and effectively become the focus of environmental protection and industry member concern.Electro-catalytic oxidation technology in the method for chemical treatment makes organic pollutant degradation, mineralising by extremely strong hydroxyl radical free radical and the processes such as the addition between the organism, replacement and transfer transport of oxidisability that electrochemical catalysis system produces, be completely oxidized to carbonic acid gas and water at last, this method has stronger oxidation capacity to the organic pollutant of bio-refractory, have non-secondary pollution, easily set up advantages such as sealing and circulating, gain great popularity in field of water treatment.In the electrocatalytic reaction process, electrode materials is in " heart " status, is the key factor that realizes electrochemical reaction and improve electrolytic efficiency.Therefore, searching and development catalytic activity height, good conductivity, anode material corrosion-resistant, that the life-span is long are the focus and emphasis of studying to reduce processing cost.
At present more employed electrode materials commonly used, as Graphite Electrodes, to organic catalyzed oxidation ability, current efficiency is low; Precious metal such as Pt, electrode costs such as Au are high and easily poisoned by materials such as sulfurous organic compounds and lose its electrocatalysis characteristic, cause oxidation current efficient sharply to descend, and are difficult to be applied in the actual engineering.Document (C.Comninellis, Preparation ofSnO
2-Sb
2O
5Films by the Spray Surpluses Technique.J.Appl.Electrochem., 1996,26:83) compared the different organism of kind more than 20 at Pt/Ti and SnO
2-Sb
2O
5Oxidation on the/Ti anode finds that the current efficiency of oxidation on the latter will be far above the former.But generally speaking, the electrocatalysis direct oxidation of titanium-based metal oxide anode is because the hydroxyl radical free radical that produces is few, and processing efficiency is unsatisfactory.In recent years, diamond film electrode is owing to have very broad electromotive force window, and very high oxygen overpotential causes extensive concern at water treatment field.Publication number is that the Chinese invention patent of CN 1336334A described is that the boron-doped diamond film electrode of substrate is used to handle waste water with the polished silicon slice, and treatment effect is better, but there are shortcomings such as bad mechanical property, specific conductivity be low in silicon.Document (Gao Chengyao etc., Ta/BDD membrane electrode electrochemical catalytic oxidation nitrophenol, Acta PhySico-Chimica Sinica, 2008, Vol 24, and No 11,1988) introduced a kind of boron-doped diamond film electrode with tantalum (Ta) substrate, electromotive force window and satisfactory stability with broad, but Ta metal fancy price is difficult to make its application that puts it over.Comparatively speaking, titanium (Ti) has cheap and the physical strength advantages of higher, document (F.Beck, W.Kaiser, H.Krohn, Boron doped diamond (BDD)-layers ontitanium substrates as electrodes in applied electrochemistry, Electrochimica Acta, 2000,45:4691) utilize Ti to carry out wastewater treatment for the boron-doped diamond film electrode of substrate, show good degradation effect, but document (Huo Sitao, the preparation research of boron doped titanium-base diamond film electrode, 2006, Institutes Of Technology Of Tianjin) titanium base diamond membrane electrode is carried out the accelerated aging test, find to have shortened its work-ing life because the existence of TiC layer causes diamond thin obscission to occur.End is got up, existing electrode materials and the preparation process ubiquity thereof that is used for wastewater treatment complex technical process, condition control inconvenience, the mechanical property of materials of its preparation is poor, specific conductivity is low, poor stability, work-ing life weak point, electromotive force window narrows, degradation property outstanding shortcoming such as low.
Summary of the invention:
The objective of the invention is to overcome the deficiency of existing electrode materials and technology of preparing existence thereof, design the processing method that a kind of preparation contains the boron doped titanium-base body diamond thin-film electrode material in tantalum middle layer, the electrode materials of this method preparation has the lower background current and the electrochemical window of broad, make the probability of organic pollutant oxidized degraded on electrode improve, and have satisfactory stability and high cost performance, can be used for poisonous and be difficult to the electrochemical treatment and the technical fields such as electroanalysis, electrosynthesis and electrical condenser of biological degradation organic pollutant.
To achieve these goals, the present invention includes titanium substrate pretreated, the preparation of tantalum middle layer and three steps of boron-doped diamond film preparation:
Substrate pretreated: preferred dimension is that the TA2 industrially pure titanium plate of Φ 20mm and Φ 50mm is done electrode matrix, and first counter electrode titanium matrix surface is polished and distilled water flushing, and the titanium matrix that obtains uniform smooth-flat-surface is standby;
The preparation of tantalum middle layer: adopting magnetron sputtering method is that Φ 50mm purity is 99.99% tantalum at the target that the titanium matrix surface coats the deposition of tantalum middle layer, fully clean with analytical pure acetone and distilled water, then at 100～120 ℃ of insulation 2～3h, remove impurity such as surface and oil contaminant, the tantalum target that to handle and titanium matrix are put into magnetic control sputtering device again, vacuumize to make sputtering chamber vacuum tightness reach 1 * 10
-4Pa, then by volume for (30～50): (60～80) continue to charge into the mixed gas that purity is the oxygen of 99.999% argon gas and 99.99% respectively, then to the pre-sputter 5min of tantalum target, after removing surface impurity, keep 100～120 ℃ of titanium substrate temperatures, again tantalum target is carried out sputter, make titanium matrix table formation of deposits tantalum middle layer;
Boron-doped diamond film preparation: when adopting hot filament CVD to prepare diamond thin, adopt bortz powder that the titanium matrix that deposits the tantalum middle layer is carried out mechanical mark earlier, make slick titanium matrix surface form fine and close uniform tiny pit, increase titanium matrix nucleation density, use the distilled water ultrasonic cleaning then, with volume ratio is (200～220): the gas mixture of (4～20) methane and hydrogen is used B as source of the gas
2H
6Be boron dopant source, power input is 1.6～2.0KW in the reaction process, underlayer temperature reaches or is higher than 800 ℃, chamber pressure 4.5～6.0KPa, the incorporation of boron in atomic ratio (B/C) the control film of boron and carbon in the change source of the gas, depositing time 5～10h is after deposition is shaped on the boron-doped diamond film again on the titanium matrix surface that coats the tantalum middle layer, as novel electrode materials.
The electrode materials that is used for degradable organic pollutant of the present invention's preparation is titanium matrix, tantalum (Ta) middle layer and diamond thin order covered structure, be coated with the tantalum middle layer with the matrix driving fit on the titanium matrix surface, deposit the boron-doped diamond film on the outer side of tantalum middle layer; Wherein the titanium matrix is an industrially pure titanium, and the purity mass percent is not less than 99%, and the thickness in compound tantalum middle layer is 1 μ m, with protection titanium matrix, suppresses the growth of TiC, prolongs electrode life; The resistivity of boron-doped diamond film is 10
9～10
12Ω cm is p type diamond thin; Boron mixes and makes film resiativity be reduced to 10
-3Ω cm rank is near the conductor scope; Adopt B
2H
6Be the boron source, carbon source is CH
4And H
2Mixed gas, the diamond film electrode for preparing electroconductibility by the control boron doping amount is used for the electrode materials of degradable organic pollutant.
The present invention compared with prior art, its technological process is simple, and is safe and reliable, the electrode materials cost performance height of preparation, wide and the good degrading effect of electromotive force window, deposition of tantalum middle layer make diamond thin difficult drop-off in electrolytic process, and the stability of diamond film electrode is high.
Description of drawings:
Fig. 1 for the electrode of the present invention preparation at 1mol/LH
2SO
4Cyclic voltammetry curve in the solution.
The COD graphic representation of Fig. 2 time sampling solution for the invention process.
Embodiment:
Also further specify method and the effect thereof that the present invention prepares electrode materials in conjunction with the accompanying drawings below by embodiment.
Embodiment:
The present embodiment preparation process comprises titanium substrate pretreated, the preparation of tantalum middle layer and three steps of boron-doped diamond film preparation:
Substrate pretreated: preferred dimension is that the TA2 industrially pure titanium plate of Φ 20mm and Φ 50mm is done electrode matrix, and first counter electrode matrix surface is polished, distilled water flushing, and it is standby to obtain uniform smooth-flat-surface titanium matrix;
The preparation of tantalum middle layer: adopting magnetically controlled sputter method is the pure tantalum (99.99%) of Φ 50mm at the target that the titanium matrix surface coats the deposition of tantalum middle layer, fully clean with analytical pure acetone and distilled water, then at 100～120 ℃ of insulation 2～3h, remove impurity such as surface and oil contaminant, the tantalum target that to handle and titanium matrix are put into magnetic control sputtering device again, vacuumize to make sputtering chamber vacuum tightness reach 1 * 10
-4Pa, then by volume for (30～50): (60～80) continue to charge into the mixed gas that purity is the oxygen of 99.999% argon gas and 99.99% respectively, then to the pre-sputter 5min of tantalum target, after removing surface impurity, keep 100～120 ℃ of titanium substrate temperatures, again tantalum target is carried out sputter, make the tantalum middle layer;
Boron-doped diamond film preparation: when adopting hot filament CVD to prepare diamond thin, adopt bortz powder that the titanium matrix that deposits the tantalum middle layer is carried out mechanical mark earlier, make slick titanium matrix surface form fine and close uniform tiny pit, increase the matrix nucleation density, use the distilled water ultrasonic cleaning then, with volume ratio is (200～220): the gas mixture of (4～20) methane and hydrogen is used B as source of the gas
2H
6Be boron dopant source, power input is 1.6～2.0KW in the reaction process, underlayer temperature reaches or is higher than 800 ℃, chamber pressure 4.5～6.0KPa, the incorporation of boron in atomic ratio (B/C) the control film of boron and carbon in the change source of the gas, depositing time 5～10h is after deposition is shaped on the boron-doped diamond film again on the titanium matrix surface that coats the tantalum middle layer, as novel electrode materials.
Present embodiment adopts four-point probe method to measure the resistivity of prepared boron-doped diamond thin-film electrode material, and when mixing a certain amount of boron, the resistivity of electrode can reach 5 * 10
-2～2 * 10
-3Ω cm has good electrical conductivity; Electrochemical window is an important indicator of weighing the electrocatalysis ability of electrode materials, adopts the electrochemical window of cyclic voltammetry test diamond membrane electrode, at 1mol/L H
2SO
4Electrolysis in the solution, scanning speed is 100mV/s, sweep interval is-2～3V, test-results is seen shown in Figure 1, the background current value of its boron-doped diamond membrane electrode is very low, and electrochemical window is about 4V, particularly reaches about 3V at the positive terminal oxidizing potential, and most of organic oxidizing potentials show that in 1.5～2.0V scope the boron-doped diamond thin-film electrode material of present embodiment preparation can be realized most of organic direct oxidations are decomposed.
Present embodiment is 2, in the 4-chlorophenesic acid electrochemical catalytic oxidation degraded test, with 2,4-chlorophenesic acid and supporting electrolyte place the container of constant temperature 500mL, with agitator electrolytic solution is stirred, in the degradation experiment 2,4-chlorophenesic acid starting point concentration is 0.1g/L, it is anode that the electrochemical catalysis degradation process adopts the diamond film electrode material, and the titanium plate is a negative electrode, and interpole gap is 2mm, constant-current electrolysis, the 1mL that takes a sample from electrolytic solution pitch time places the measurement to be analyzed of clean dried pipe, and chemical oxygen demand (COD) in the experiment (COD) is measured and adopted GDYS-101SQ COD determination instrument to measure, with the COD of degradation process
tWith original value COD
0Weigh degradation effect, test result as shown in Figure 2, the result shows, when the organic concentration in the experiment initial stage solution is higher, electrolytic speed is very fast, the fall of COD is big, drop to 11000mg/L rapidly by 28800mg/L, but along with carrying out gradually of experiment, the COD rangeability reduces and tends towards stability gradually, and the COD value finally can drop to 100mg/L, shows that the boron-doped diamond thin-film electrode material of present embodiment preparation has excellent organic pollutant degradation effect, be suitable for handling the high concentration organic contaminant waste water of the reluctant COD value of conventional electrochemical electrode, show good degradation capability and COD clearance up to several ten thousand mg/L.
In order to measure the stability of boron-doped diamond membrane electrode, present embodiment uses Ti/Ta/BDD electrode and Ti/BDD electrode as anode respectively, and the titanium plate is a negative electrode, at 1mol/L H
2SO
4Apply 1A/cm in the solution
2Current density, the intensified electrolysis time, the diamond thin obscission appearred in the Ti/BDD electrode when being 700h, and the Ti/Ta/BDD electrode surface is still intact, XRD and Raman spectrum test result show Ti/Ta/BDD electrode surface sp
3The diamond of structure is constant substantially mutually, and electrode shows advantages of higher stability.
Claims (2)
1. the electrode materials preparation method of a degradable organic pollutant is characterized in that comprising titanium substrate pretreated, the preparation of tantalum middle layer and three steps of boron-doped diamond film preparation:
Substrate pretreated: preferred dimension is that the TA2 industrially pure titanium plate of Φ 20mm and Φ 50mm is done electrode matrix, and first counter electrode titanium matrix surface is polished and distilled water flushing, and the titanium matrix that obtains uniform smooth-flat-surface is standby;
The preparation of tantalum middle layer: adopting magnetron sputtering method is that Φ 50mm purity is 99.99% tantalum at the target that the titanium matrix surface coats the deposition of tantalum middle layer, fully clean with analytical pure acetone and distilled water, then at 100～120 ℃ of insulation 2～3h, remove impurity such as surface and oil contaminant, the tantalum target that to handle and titanium matrix are put into magnetic control sputtering device again, vacuumize to make sputtering chamber vacuum tightness reach 1 * 10
-4Pa, then by volume for (30～50): (60～80) continue to charge into the mixed gas that purity is the oxygen of 99.999% argon gas and 99.99% respectively, then to the pre-sputter 5min of tantalum target, after removing surface impurity, keep 100～120 ℃ of titanium substrate temperatures, again tantalum target is carried out sputter, make titanium matrix table formation of deposits tantalum middle layer;
Boron-doped diamond film preparation: when adopting hot filament CVD to prepare diamond thin, adopt bortz powder that the titanium matrix that deposits the tantalum middle layer is carried out mechanical mark earlier, make slick titanium matrix surface form fine and close uniform tiny pit, increase titanium matrix nucleation density, use the distilled water ultrasonic cleaning then, with volume ratio is (200～220): the gas mixture of (4～20) methane and hydrogen is used B as source of the gas
2H
6Be boron dopant source, power input is 1.6～2.0KW in the reaction process, underlayer temperature reaches or is higher than 800 ℃, chamber pressure 4.5～6.0KPa, the incorporation of boron in atomic ratio (B/C) the control film of boron and carbon in the change source of the gas, depositing time 5～10h, after deposition is shaped on the boron-doped diamond film again on the titanium matrix surface that coats the tantalum middle layer as electrode materials.
2. the electrode materials preparation method of degradable organic pollutant according to claim 1, it is characterized in that the electrode materials that is used for degradable organic pollutant for preparing is titanium matrix, tantalum (Ta) middle layer and diamond thin order covered structure, be coated with the tantalum middle layer with the matrix driving fit on the titanium matrix surface, deposit the boron-doped diamond film on the outer side of tantalum middle layer; Wherein titanium matrix purity mass percent is not less than 99%, and the thickness in compound tantalum middle layer is 1 μ m, with protection titanium matrix, suppresses the growth of TiC, prolongs electrode life; The resistivity of boron-doped diamond film is 10
9～10
12Ω cm is p type diamond thin; Boron mixes and makes film resiativity be reduced to 10
-3Ω cm is near the conductor scope; Adopt B
2H
6Be the boron source, carbon source is CH
4And H
2Mixed gas, the diamond film electrode for preparing electroconductibility by the control boron doping amount is used for the electrode materials of degradable organic pollutant.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102174704A (en) * | 2011-02-20 | 2011-09-07 | 中国船舶重工集团公司第七二五研究所 | Preparation method for tantalum-contained interlayer metallic oxide electrode |
| CN102242374A (en) * | 2011-06-30 | 2011-11-16 | 南京航空航天大学 | Production method of titanium-based boron-doping diamond coating electrode |
| CN103215614A (en) * | 2013-04-27 | 2013-07-24 | 中国船舶重工集团公司第七二五研究所 | Preparation method of metallic oxide anode containing cold spraying tantalum intermediate layer |
| CN104528892A (en) * | 2015-01-08 | 2015-04-22 | 深圳盖雅环境科技有限公司 | Method and application for boron-doped diamond electrode with maximum indirect oxidation efficiency prepared by hot-filament method |
| CN104977348A (en) * | 2015-07-22 | 2015-10-14 | 南京林业大学 | Method for predicating perdurable stability of organic pollutants |
| CN105502595A (en) * | 2016-02-19 | 2016-04-20 | 周检 | Titanium-based positive electrode with high oxygen evolution overpotential and preparing method thereof |
| CN108602699A (en) * | 2016-02-05 | 2018-09-28 | 西门子能源有限公司 | Electroxidation at an elevated pressure |
| CN108726642A (en) * | 2018-06-05 | 2018-11-02 | 浙江大学 | Utilize the method for persistent organic pollutants in BDD electrode activation sulfate efficient degradation neutral and alkali waste water |
| CN109750291A (en) * | 2017-11-07 | 2019-05-14 | 深圳先进技术研究院 | A kind of boron-doped diamond electrode and preparation method thereof |
| CN111675417A (en) * | 2020-05-11 | 2020-09-18 | 江苏净钻环保科技有限公司 | Magnetic adsorption assisted photoelectrocatalysis oxidation water treatment system and water treatment method |
| CN111948266A (en) * | 2020-08-18 | 2020-11-17 | 中国地质大学（北京） | Self-supporting boron-doped diamond electrochemical sensor and preparation method and application thereof |
| CN112607831A (en) * | 2020-12-17 | 2021-04-06 | 江苏羟源环能科技有限公司 | Active element uniformly-doped thin film electrode and preparation method thereof |
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| CN102174704A (en) * | 2011-02-20 | 2011-09-07 | 中国船舶重工集团公司第七二五研究所 | Preparation method for tantalum-contained interlayer metallic oxide electrode |
| CN102242374A (en) * | 2011-06-30 | 2011-11-16 | 南京航空航天大学 | Production method of titanium-based boron-doping diamond coating electrode |
| CN103215614A (en) * | 2013-04-27 | 2013-07-24 | 中国船舶重工集团公司第七二五研究所 | Preparation method of metallic oxide anode containing cold spraying tantalum intermediate layer |
| CN103215614B (en) * | 2013-04-27 | 2015-05-27 | 中国船舶重工集团公司第七二五研究所 | Preparation method of metallic oxide anode containing cold spraying tantalum intermediate layer |
| CN104528892B (en) * | 2015-01-08 | 2016-08-17 | 深圳盖雅环境科技有限公司 | Heat wire method preparation has method and the application of the boron-doped diamond film electrode of maximum indirect oxidation efficiency |
| CN104528892A (en) * | 2015-01-08 | 2015-04-22 | 深圳盖雅环境科技有限公司 | Method and application for boron-doped diamond electrode with maximum indirect oxidation efficiency prepared by hot-filament method |
| CN104977348A (en) * | 2015-07-22 | 2015-10-14 | 南京林业大学 | Method for predicating perdurable stability of organic pollutants |
| CN108602699A (en) * | 2016-02-05 | 2018-09-28 | 西门子能源有限公司 | Electroxidation at an elevated pressure |
| CN108602699B (en) * | 2016-02-05 | 2021-04-27 | 西门子能源美国公司 | Electrooxidation at elevated pressure |
| CN105502595A (en) * | 2016-02-19 | 2016-04-20 | 周检 | Titanium-based positive electrode with high oxygen evolution overpotential and preparing method thereof |
| CN109750291A (en) * | 2017-11-07 | 2019-05-14 | 深圳先进技术研究院 | A kind of boron-doped diamond electrode and preparation method thereof |
| CN108726642A (en) * | 2018-06-05 | 2018-11-02 | 浙江大学 | Utilize the method for persistent organic pollutants in BDD electrode activation sulfate efficient degradation neutral and alkali waste water |
| CN111675417A (en) * | 2020-05-11 | 2020-09-18 | 江苏净钻环保科技有限公司 | Magnetic adsorption assisted photoelectrocatalysis oxidation water treatment system and water treatment method |
| CN111948266A (en) * | 2020-08-18 | 2020-11-17 | 中国地质大学（北京） | Self-supporting boron-doped diamond electrochemical sensor and preparation method and application thereof |
| CN112607831A (en) * | 2020-12-17 | 2021-04-06 | 江苏羟源环能科技有限公司 | Active element uniformly-doped thin film electrode and preparation method thereof |
| CN112607831B (en) * | 2020-12-17 | 2022-12-23 | 江苏羟源环能科技有限公司 | Active element uniformly-doped thin film electrode and preparation method thereof |
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