EP2657370A1 - Elektrisch leitfähige diamantelektrode sowie schwefelsäure-elektrolyseverfahren und schwefelsäure-elektrolysevorrichtung damit - Google Patents

Elektrisch leitfähige diamantelektrode sowie schwefelsäure-elektrolyseverfahren und schwefelsäure-elektrolysevorrichtung damit Download PDF

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Publication number
EP2657370A1
EP2657370A1 EP11851375.3A EP11851375A EP2657370A1 EP 2657370 A1 EP2657370 A1 EP 2657370A1 EP 11851375 A EP11851375 A EP 11851375A EP 2657370 A1 EP2657370 A1 EP 2657370A1
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Prior art keywords
electrically conductive
conductive diamond
anode
sulfuric acid
electrolysis
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English (en)
French (fr)
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EP2657370A4 (de
Inventor
Masaaki Kato
Hiroki Domon
Junko Kosaka
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De Nora Permelec Ltd
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Chlorine Engineers Corp Ltd
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/042—Electrodes formed of a single material
    • C25B11/043—Carbon, e.g. diamond or graphene
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/28—Per-compounds
    • C25B1/29—Persulfates
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/28—Per-compounds
    • C25B1/30—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C25B11/083—Diamond
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms

Definitions

  • the present invention relates to an electrically conductive diamond electrode, and a sulfuric acid electrolysis method and a sulfuric acid electrolysis apparatus each utilizing same which stably form oxidizing agent through direct electrolysis of sulfuric acid applying the electrically conductive diamond electrode.
  • Persulfuric acid and persulfate have been used in various manufacturing and inspection processes as chemical agents, such as pre-treatment agent for electrolytic metal plating, etching agent, oxidizing agent in chemical and mechanical polishing treatment for semiconductor device manufacturing, oxidizing agent for organic substance in wet analyses, and cleaning agent for silicon wafer.
  • chemical agents such as pre-treatment agent for electrolytic metal plating, etching agent, oxidizing agent in chemical and mechanical polishing treatment for semiconductor device manufacturing, oxidizing agent for organic substance in wet analyses, and cleaning agent for silicon wafer.
  • oxidizing agent which are called “oxidizing agent”
  • oxidizing agent are known to be formed by electrolysis of sulfuric acid, and have been electrolytically manufactured in an industrial scale.
  • the "oxidizing agent” indicates persulfuric acid which names generically peroxodisulfuric acid and peroxomonosulfuric acid and hydrogen peroxide.
  • the “oxidizing agent” which is an electrolysis product, is used for cleaning or surface treatment of components, a method to produce a chemical solution with a high concentration is required, since in most cases, the higher the total concentration is, the higher the effect obtained from it becomes.
  • electrolysis process is applied, where it is effective for high productivity to maintain the electric power consumption rate calculated from cell voltage, electrolytic current and current efficiency to be low and to keep a high current efficiency stably over time in order to save energy required for the production.
  • a manufacturing method of a highly durable electrode for long life and for production of clean electrolyte free from pollution from the electrode is required.
  • PTL 1 discloses a sulfuric acid electrolysis method for manufacturing persulfuric acid through electrolysis of concentrated sulfuric acid applying an electrically conductive diamond anode and a cleaning method to rinse silicon wafer work piece applying produced persulfuric acid.
  • This electrically conductive diamond electrode is superior in efficiency of electrolytic oxidation of sulfuric acid to persulfuric acid because it has a larger overvoltage of oxygen generation compared with a platinum electrode so far used widely as electrode to form persulfate.
  • the electrically conductive diamond electrode features chemically stable property and a long life as electrode.
  • the electrically conductive diamond electrode has a higher current efficiency of persulfuric acid and a higher durability, compared with other electrode catalysts (Pt, PbO 2 , etc.), and can produce clean electrolyte free from pollution from the electrode.
  • the application of the electrically conductive diamond electrode is being promoted in the areas, such as manufacturing cleaning solution for semiconductor wafer.
  • PTL 1 only discloses a method relating to a sulfuric acid electrolysis method applying an electrically conductive diamond anode to produce persulfuric acid through electrolysis of concentrated sulfuric acid, in which cleaning solution containing persulfuric acid is formed by electrolyzing concentrated sulfuric acid, the cleaning solution is supplied to the materials to be rinsed such as silicon water with resist, the used cleaning solution with decreased concentration of persulfuric acid is recovered for successive electrolysis, and the same cleaning solution with increased concentration of persulfuric acid is used cyclically for cleaning, without disclosing the relation between the crystallinity of the electrically conductive diamond electrode and the Raman spectrometry property ⁇ potential window, and the relation between the crystallinity of the electrically conductive diamond electrode and the productivity in terms of the current efficiency, cell voltage, etc. of persulfuric acid like peroxodisulfuric acid or the oxidizing agent in the cleaning solution.
  • PTL 2 discloses the methods to maintain a high strength of the diamond by prescribing the diamond layer thickness and to enhance abrasion resistance of the diamond by prescribing the peak intensity ratio of Raman spectrometry, as polycrystalline diamond for tools. Further, it is specified that the diamond described in PTL 2 should have a layer thickness of 50 ⁇ m or more and the peak ratio of the diamond carbon and non-diamond carbon (non-diamond carbon/diamond carbon) by Raman spectroscopic analysis being within a range of 2.0 or less.
  • This diamond is not an electrode for electrolysis, and there is no disclosure about the correlation between the crystallinity of the electrically conductive diamond electrode and the potential window as one of properties of electrolysis, or about the relation of the crystallinity with productivity in terms of current efficiency or cell voltage of persulfuric acid as peroxodisulfuric acid or oxidizing agent in the cleaning solution
  • PTL 3 discloses an electrically conductive diamond electrode having an electrically conductive layer of electrically conductive diamond-like carbon as an electrode for the electrolysis for an ozone water production apparatus.
  • the electrically conductive layer described in PTL 3 has the ratio of the integrated intensity Int ⁇ 1340> of the peak present at 1340cm -1 ⁇ 20cm -1 to the integrated intensity Int ⁇ 1580> of the peak present at 1580cm -1 ⁇ 20cm -1 in Raman spectroscopic analysis which satisfies the following equation.
  • Int ⁇ 1340 > / Int ⁇ 1580 > 0.5 ⁇ 1.5
  • PTL 3 explicitly describes that diamond-like carbon indicates amorphous hard carbon, different in structure from an electrically conductive diamond having a crystalline structure.
  • PTL 3 applying diamond-like carbon as electrode gives no disclosure about the relation between the crystallinity of the electrically conductive diamond electrode and the Raman spectrometry property ⁇ potential window, and the relation between the crystallinity of the electrically conductive diamond electrode and the productivity in terms of current efficiency, cell voltage, etc. of persulfuric acid like peroxodisulfuric acid and the oxidizing agent in the cleaning solution.
  • the present invention aims to solve the problems of the conventional technologies and to provide an electrically conductive diamond electrode featuring a high durability as electrode and a high current efficiency of oxidizing agent at a low cell voltage, an electrolysis method of sulfuric acid and an electrolysis apparatus for sulfuric acid, applying the electrically conductive diamond electrode.
  • Inventors of the present invention have found from their extensive studies to solve the problems that the crystallinity of the electrically conductive diamond has a close relationship with electrolysis performance including durability of electrode, cell voltage and current efficiency of oxidizing agent, and have succeeded in achieving aimed electrolysis performance by evaluating the crystallinity from the thickness of the electrically conductive diamond layer, the range of the potential window and the peak intensity ratio of the Raman spectrometry.
  • the present invention provides an electrically conductive diamond electrode comprising an electrically conductive substrate and an electrically conductive diamond layer coated on the surface of the electrically conductive substrate, featuring that:
  • the present invention provides the electrode applying the electrically conductive diamond layer containing boron in the range of 1000 ⁇ 6000 ppm.
  • the present invention provides the electrode applying the silicon substrate as an electrically conductive substrate.
  • the present invention provides a sulfuric acid electrolysis method in which an anode compartment is separated from a cathode compartment by a diaphragm, an electrically conductive diamond anode is installed in the anode compartment, a cathode is installed in the cathode compartment, electrolyte containing sulfate ion is supplied respectively to the anode compartment and the cathode compartment from the outside, and oxidizing agent is formed in the anode electrolyte in the anode compartment by electrolysis, wherein a special electrically conductive diamond electrode is applied as electrically conductive diamond electrode and the concentration of sulfate ion in the electrolyte containing sulfate ion is in the range of 2 ⁇ 14 mol/l.
  • the present invention provides a sulfuric acid electrolysis method wherein the concentration of acid in the electrolyte containing sulfate ion under the afore-mentioned electrolysis conditions is in the range of 4 ⁇ 28 mol/l.
  • the present invention provides a sulfuric acid electrolysis apparatus in which an anode compartment is separated from a cathode compartment by a diaphragm, an electrically conductive diamond anode is installed in the anode compartment, a cathode is installed in the cathode compartment, electrolyte containing sulfate ion is supplied respectively to the anode compartment and the cathode compartment from the outside, and oxidizing agent is formed in the anode electrolyte in the anode compartment by electrolysis, wherein the afore-mentioned electrically conductive diamond electrode is applied and a fluororesin type cation exchange membrane or a hydrophilically treated porous fluororesin membrane is applied as diaphragm.
  • An electrically conductive diamond electrode, and a sulfuric acid electrolysis method and a sulfuric acid electrolysis apparatus applying the electrically conductive diamond electrode by the present invention can manufacture a solution of oxidizing agent with a high concentration at a low cell voltage and at a high current efficiency using an electrode with a high durability, which have not been achieved by the conventional technology.
  • the present invention has found that a close relationship exists between the crystallinity of the electrically conductive diamond electrode and the durability of the electrode, cell voltage, concentration of oxidizing agent of the produced oxidizing agent solution of oxidizing agent, and current efficiency, when sulfuric acid is electrolyzed by an electrolysis cell in which the electrically conductive diamond electrode is incorporated.
  • Diamond is a cubic crystal in which each constituent carbon atom connects by SP3 hybrid orbital and an insulator with a large band gap.
  • the electrically conductive diamond in the present invention indicates a diamond provided with conductivity by doping impurities with different valency from carbon. From a viewpoint of raising conductivity, the concentration of impurities should be high, but if it is too high, crystallinity collapses and the electrode looks as if soot attaches to and durability becomes poor.
  • the crystallinity in the present invention represents a regularity of crystal sequence or the content of impurities other than carbon. More specifically, crystallinity becomes low when there are many components of non-diamond, graphite, and amorphous diamond, when the electrically conductive diamond layer is thin, when the particle size of electrically conductive diamond is small and when there is much content of the impurity elements other than carbon.
  • the present invention constitutes an electrically conductive diamond electrode which features that the thickness of the electrically conductive diamond layer is in the range of 1 ⁇ 25 ⁇ m, the potential window fulfills Equation (1), and the ratio (A/B) of the diamond component A and non-diamond component B by the Raman spectroscopic analysis fulfills Equation (2).
  • Equation (1) the ratio (A/B) of the diamond component A and non-diamond component B by the Raman spectroscopic analysis fulfills Equation (2).
  • the thickness of the electrically conductive diamond layer preferably is in the range of 1 ⁇ 25 ⁇ m, more preferably 1 ⁇ 15 ⁇ m.
  • the layer thickness of the electrically conductive diamond electrode by the present invention is preferably in the range of 1 ⁇ 25 ⁇ m
  • the potential window in the present invention indicates the electric potential region where generation of neither hydrogen nor oxygen occurs in water electrolysis reactions.
  • the potential window is wide, the crystallinity of electrically conductive diamond layer becomes high and the durability of electrode enhances.
  • the width of potential window is greater than 3.5V, the current efficiency of oxidizing agent decreases and the cell voltage increases.
  • the width of the potential window is narrower than 2.1 V, the durability of the electrode deteriorates.
  • the crystallinity of electrically conductive diamond layer becomes high and the durability of electrode enhances.
  • the peak intensity ratio A/B by the Raman spectrometry is larger than 6.5, the current efficiency of oxidizing agent lowers and the cell voltage increases.
  • the peak intensity ratio A/B by the Raman spectrometry is small, the crystallinity of electrically conductive diamond layer decreases, the efficiency of oxidizing agent increases and the cell voltage decreases.
  • the durability of the electrode decreases when the peak intensity ratio A/B by the Raman spectrometry is 1.5 or less.
  • the electrically conductive diamond layer contains boron in the range of preferably 1000 ⁇ 6000 ppm, more preferably 3000 ⁇ 5000 ppm.
  • the boron concentration becomes too high, more than 6000 ppm the electrode looks as if soot attaches to and the durability of electrode decreases. Then, the electrically conductive diamond electrode by the present inventions should contain boron in the range of 1000 ⁇ 6000 ppm.
  • an electrically conductive substrate there is no specific restriction and such materials as tantalum, tungsten, titanium and niobium are applicable.
  • a silicon substrate provides an electrode with superior adhesion.
  • there is no restriction to the shape of the electrically conductive substrate allowing plate, rod, pipe or spherical type.
  • the electrically conductive substrate can contain impurities, such as boron and carbon.
  • Fig.1 shows one example of the electrolysis cell used for the sulfuric acid electrolysis method and the sulfuric acid electrolysis apparatus by the present invention.
  • the electrolysis cell is divided by the porous PTFE diaphragm 9 into the anode compartment 3 accommodating the electrically conductive diamond anode 10 filled with electrolyte containing sulfate ion and the cathode compartment 4 accommodating the electrically conductive diamond cathode 12 filled with sulfuric acid solution with the same concentration as that in the anode compartment 3.
  • the anolyte inlet 7 is connected, through which sulfuric acid which is anolyte is supplied to the anode compartment 3.
  • the catholyte inlet 8 is connected, through which catholyte is supplied to the cathode compartment 4.
  • the oxidizing agent solution formed in the anode compartment 3 is discharged from the anolyte outlet 1.
  • Hydrogen and sulfuric acid solution formed in the cathode compartment 4 are discharged from the catholyte outlet 2.
  • Other components include the anode power supply terminal 5, the cathode power supply terminal 6, the electrically conductive substrate 11 of the electrically conductive diamond anode 10, the electrically conductive substrate 13 of the electrically conductive diamond cathode 12, the sealing material 14 of the electrolysis cell, the cooling jacket 15, the cooling water outlet 16 and the cooling water inlet 17.
  • the electrically conductive diamond anode 10 and the electrically conductive diamond cathode 12 by the present invention comprise the electrically conductive diamond layer coated on the surfaces of the electrically conductive substrates 11, 13.
  • the coating method of the electrically conductive diamond layer is not necessarily limited. Typical methods optionally applicable include the hot filament CVD method, the microwave plasma CVD method and the DC arc jet plasma CVD method.
  • a cathode made of platinum and others can be used instead of the electrically conductive diamond cathode 12.
  • the electrolyte containing sulfate ion (HSO 4 - or SO 4 2- ) for the present invention should contain sulfate ion in the range of 2 ⁇ 14 mol/l, more preferably 3 ⁇ 9 mol/l. If the concentration of sulfate ion (HSO 4 - or SO 4 2- ) is smaller than 2 mol/l, the current efficiency of oxidizing agent decreases because of reduced reactant. If the concentration of sulfate ion is larger than 14 mol/l, the viscosity of electrolyte increases, gas liberation becomes poor, the bubble fraction increases and the conductivity of electrolyte decreases, leading to the increase of cell voltage. For this reason the present invention specifies the concentration of sulfate ion in the electrolyte containing sulfate ion to the range of 2 ⁇ 14 mol/l.
  • the acid (H + ) concentration of the electrolyte containing sulfate ion for the present invention is in the range of 4 ⁇ 28 mol/l, more preferably 6 ⁇ 18 mol/l. If the acid (H + ) concentration is smaller than 4 mol/l, the conductivity of electrolyte is low and the cell voltage increases. On the other hand if the acid concentration (H + ) is larger than 28 mol/l, the current efficiency of oxidizing agent decreases. For this reason the present invention specifies the acid concentration to the range of 4 ⁇ 28 mol/l.
  • A/I current /anolyte volume
  • the present invention specifies the range to 100 ⁇ X ⁇ 10000 and 25 ⁇ Y ⁇ 250.
  • the porous PTFE diaphragm 9 separates the anode compartment 3 from the cathode compartment 4 and let conductivity be generated by ion exchange action or moving of electrolyte between the anode compartment 3 and the cathode compartment 4 through apertures in the diaphragm.
  • the constitution materials are not limited in particular, but in view of durability, it is desirable to use a diaphragm comprising fluororesin type cation exchange membrane or hydrophilically treated porous fluororesin type membrane.
  • the oxidizing agent is electrolytically reduced at the cathode and the concentration of oxidizing agent decreases. For this reason, it is desirable to provide the porous PTFE diaphragm 9.
  • the constitution materials for the parts which are in contact with sulfuric acid electrolyte are not limited in particular, but desirable are such materials as fluororesin like PTFE and PFA, glass and quartz, having resistivity to sulfuric acid.
  • the electrolyte containing sulfate ion in the present invention may include impurities other than sulfate ion. Electrolyte comprising sulfuric acid or sulfates like ammonium sulfate and water is desirable in view of high current efficiency in the production of persulfuric acid. Whereas, it is not desirable to include organic substance because it reacts with oxidizing agent formed by the electrolysis, which will be a cause for decreasing the concentration of the oxidizing agent of the electrolyte. In case that the oxidizing agent is used for the washing material in the production of semiconductor device, it is preferable not to include metal ion because metal adversely affects the device as an impurity.
  • the electrolysis temperature it is preferable to control the electrolysis temperature to the range of 0-50 degrees Celsius.
  • circulation of electrolyte is optional. In view of effective cooling of the electrolyte, circulation is preferable.
  • the anolyte volume means the sum of the anolyte on the anode side within the circulation apparatus including electrolysis cell, piping, gas-liquid separation tank, and pumps.
  • the present invention include the case of "one-pass", in which electrolyte is passed once through the electrolysis cell without being circulated.
  • the anolyte volume means the volume of electrolyte on the side of anode present within the electrolytic cell.
  • Fig.2-1 shows an example of the sulfuric acid electrolysis method and the sulfuric acid electrolysis apparatus by the present invention, in which sulfuric acid is electrolyzed while anolyte and catholyte are being circulated.
  • Electrolyte containing sulfate ion is supplied to the anode compartment 3 of the electrolysis cell 21 from the anolyte feed line 18 by means of the anolyte feed pump 19 and the flow meter 20, electrolyzed in the anode compartment 3 and circulated through the circulation line 25 to the anode compartment 3 by means of the flow meter 22 and the anolyte circulation/discharge pump 23.
  • the generated gas is separated by the gas-liquid separator on the anode side 26 and discharged from the generated gas outlet 27.
  • the produced solution of oxidizing agent is discharged through the oxidizing agent solution discharge line 24 by means of the flow meter 22 and the anolyte circulation/discharge pump 23.
  • the electrolyte containing sulfate ion is supplied to the cathode compartment 4 of the electrolysis cell 21 through the catholyte feed line 28 by means of the catholyte feed pump 29 and the flow meter 30, electrolyzed in the cathode compartment 4 and circulated to the cathode compartment 4 through the catholyte circulation line 34 by means of the flow meter 31 and the catholyte circulation/discharge pump 32.
  • the generated gas is separated by the gas-liquid separator on the cathode side 35 and discharged from the generated gas outlet 36.
  • the catholyte is discharged through the catholyte outlet line 33 by means of the flow meter 31 and the catholyte circulation/discharge pump 32.
  • the electrolysis cell 21 is cooled by the cooling jacket 15 and the cooling water circulation line 37. The temperature of electrolyte is measured at the anolyte outlet 1 illustrated in Fig.1 .
  • Fig. 2-2 shows another example of the sulfuric acid electrolysis method and the sulfuric acid electrolysis apparatus by the present invention, in which only catholyte is circulated, with no circulation of anolyte to produce the solution of oxidizing agent in the one-pass process.
  • the explanation of the process of Fig. 2-2 is omitted because the process of Fig. 2-2 is exactly the same as Fig. 2-1 , applying the same numerals, except that in Fig.2-2 , the anolyte is not circulated and the solution of oxidizing agent is produced in one-pass process.
  • Measurement of the Raman spectrometry characteristics of the electrode prepared by the present invention measurement of the thickness of the electrically conductive diamond electrode layer, measurement of the boron concentration, the durability test of the electrode, measurement of the potential window, preparation of electrolyte containing sulfate ion used for the electrolysis, and measurement of the concentration of oxidizing agent of the produced solution of oxidizing agent are conducted by the methods described below.
  • the Raman spectrometry of the electrode surface was conducted to confirm that the electrically conductive diamond had been prepared and to measure the A/B intensity ratio.
  • the longest length of the electrode which is the full span from the both edges of the electrically conductive diamond electrode was divided and cut equally into 5 portions of the substrate. At least one single section of all cut samples obtained was observed and photographed at an accelerating voltage of 10 kV and 8000 magnifications using the scanning electron microscope (Brand Name : JSM6490 manufactured by JEOL Ltd.), and the layer thickness was obtained from the mean.
  • the surface of the prepared electrode was measured using the secondary ion mass spectrometer (Brand name: PHI ADEPT1010 manufactured by Ulvac-Phi Inc.) with O 2 + as primary ion, primary ion energy of 3keV, detection domain 100 ⁇ m ⁇ , and secondary ion polarity positive.
  • the concentration conversion was made in such a manner that the reference density standard of B in SiC composition was also measured and obtained relative sensitivity coefficient was substitutively applied to the sample.
  • oxidizing agent solution was formed on the conditions given below by the sulfuric acid electrolysis apparatus as shown in Fig. 2-1 , in which the electrolysis cell 21 with a diaphragm as shown in Fig. 1 was installed.
  • the oxidation- reduction potential was measured by means of cyclic voltammogram. More in detail, electric potential was measured applying 4.2 mol/l of sulfuric acid as electrolyte, an electrode with electrically conductive diamond layer formed on the substrate as working electrode, a platinum wire as counter electrode, mercurous sulphate reference electrode, at the time when electric current of ⁇ 50 mA/dm 2 flew at 50 mV/s of potential sweeping and the potential window was determined from the value of oxidation-reduction potential.
  • the electrically conductive diamond electrode by the present invention was manufactured in the following manner.
  • a electrically conductive substrate, which was single-crystal Si was installed in the device, after the surface of the substrate was polished, washed and treated for diamond particles seeding. While hydrogen, methane and Ar+ trimethyl borate were being supplied as introduction gas at 5 l/min. and the pressure inside the device was maintained at 60 Torr, electric power was applied to the filament and the temperature was raised to 2300 degrees Celsius. At this time, the temperature of the substrate was 800 degrees Celsius.
  • Trimethyl borate was introduced into the device by bubbling Ar into the container filled with liquid trimethyl borate.
  • the quality of layer was changed by changing the flow rates of methane and trimethyl borate.
  • the thickness of the layer was changed by changing the time for forming the layer.
  • the solution of oxidizing agent was produced by electrolyzing sulfuric acid on the conditions to be described, using the sulfuric acid electrolysis apparatus with diaphragm installed as shown in Fig. 2-1 incorporating the electrolysis cell 21 applying the electrically conductive diamond electrode with an electrolysis area of 1.000 dm 2 for both anode and cathode as shown in Fig.1 while anolyte and catholyte were being circulated. Characteristics of the prepared electrode are shown in Table 1.
  • oxidizing agent was performed on the conditions of Table 1 and those of the following, using the electrolytic cell with diaphragm applying prepared electrodes both for the anode and the cathode.
  • a 98 % sulfuric acid (manufactured by Kanto Chemical Co., Inc.) was taken by 403 g in a 1 liter measuring flask, to which hyperpure water was added to dilute to 1 liter in total to prepare electrolyte containing 4.2 mol/l of sulfate ion. From it, 300 ml was used as anolyte and 300 ml was used as catholyte. Based on Equation (7), the acid concentration was calculated to be 18.4 mol/l.
  • the results of the obtained oxidizing agent solution are given in Table 6 and as below.
  • titration was performed according to the measuring method of the concentration for the oxidizing agent.
  • the solution became colorless when 0.02 mol/I sodium thiosulfate solution was dropped by 44.00 ml. Further, the measurement repeated twice in the same manner and the results were, respectively 44.00 ml and 44.00 ml.
  • Applying the mean value of 44.00 ml the concentration of oxidizing agent was calculated from Equation (8), and 1.10 mol/l was obtained. Current efficiency was calculated by Equation (9), applying the concentration of oxidizing agent and 53% was obtained.
  • the oxidizing agent solution was obtained by the same method as described in Example 1, except that the electrode applied as anode was changed as in Tables 1 and 2 regarding the thickness of electrically conductive diamond layer, the potential window, the A/B, and the boron concentration by changing the methane flow rate, the trimethyl borate flow rate and the layer forming time was applied.
  • the results of the obtained oxidizing agent solution are given in Tables 6 and 7.
  • the oxidizing agent solution was obtained by the same method as described in Example 1, except that the sulfate ion concentration and the acid concentration in the electrolyte were changed as described in Tables 2 ⁇ 3. The results of the obtained oxidizing agent solution are given in Tables 7 and 8.
  • the oxidizing agent solution was obtained by the same method as described in Example 1, except that the anolyte volume, the current value/anolyte volume, and the electrolysis time were changed as in Table 3, and that the anolyte circulation was not performed, that is, one pass of anolyte applied, using the sulfuric acid electrolysis apparatus as shown in Fig. 2-2 , which incorporated the electrolysis cell 21 with diaphragm applying the electrically conductive diamond electrode with 1.000 dm 2 of the electrolysis area as anode and cathode as shown in Fig.1 .
  • the results of the obtained oxidizing agent solution are given in Table 8.
  • the oxidizing agent solution was obtained by the same method as described in Example 1, except that the anolyte volume, the current value/anolyte volume, the electrolysis time and the electric quantity per unit volume were changed as described in Tables 3 and 4.
  • the results of the obtained oxidizing agent solution are given in Tables 8 and 9.
  • the oxidizing agent solution was obtained by the same method as described in Example 1, except that niobium was applied as the substrate material.
  • the results of the obtained oxidizing agent solution are given in Table 9.
  • the oxidizing agent solution was obtained by the same method as described in Example 1, except that the electrode applied as anode was changed as in Table 5 regarding the thickness of electrically conductive diamond layer, the potential window, and the A/B by changing the methane flow rate, the trimethyl borate flow rate and the layer forming time.
  • the results of the obtained oxidizing agent solution are given in Table 10.
  • Comparative Example 1 desirable results were obtained in terms of cell voltage and current efficiency of the oxidizing agent, but it was visually observed after the durability test of the electrode that most of the layer of the electrode surface had been exfoliated.
  • Comparative Example 2 degradation of the layer was not confirmed from visual observation of the electrode surface after the durability test of the electrode, but the cell voltage during electrolysis was high and the current efficiency from the obtained solution containing oxidizing agent was revealed to be low.
  • Comparative Example 3 desirable results were obtained in terms of cell voltage and current efficiency, but it was visually observed after the durability test of the electrode that most of the layer of the electrode surface had been exfoliated.
  • Comparative Example 4 degradation of the layer of the electrode was not confirmed from visual observation after the durability test of the electrode, but the cell voltage during electrolysis was high and the current efficiency from the obtained solution containing oxidizing agent was revealed to be low.
  • Comparative Example 5 degradation of the electrode was observed during electrolysis, and carbon powder was visually confirmed in the electrolyte and electrolysis was suspended.
  • Example 1 Example 2
  • Example 3 Example 4
  • Example 5 Anode and Cathode Coating Material Electrically conductive Diamond Substrate Material Electrically conductive Silicon Diamond Layer Thickness ( ⁇ m) 10 10 10 10 1.5 23 Potential Window (V) 2.63 2.12 3.40 2.80 2.12 3.30 A/B 4.50 1.80 6.20 6.30 1.58 6.00 Conc. of Boron (ppm) 3000 3000 3000 3000 3000 Conc. of Sulfate Ion in Electrolyte (mol/l) 4.2 4.2 4.2 4.2 4.2 4.2 4.2 Conc.
  • Example 7 Example 8
  • Example 9 Example 10
  • Example 11 Anode and Cathode Coating Material Electrically conductive Diamond Substrate Material Electrically conductive Silicon Diamond Layer Thickness ( ⁇ m) 10 10 10 10 10 10 10 Potential Window (V) 3.50 3.20 2.60 2.15 2.63 2.63 A/B 6.00 5.50 3.20 1.62 4.50 4.50 Conc. of Boron (ppm) 700 1200 5000 7000 3000 3000 Conc. of Sulfate Ion in Electrolyte (mol/l) 4.2 4.2 4.2 4.2 1.9 2.5 Conc.
  • Example 13 Example 14
  • Example 15 Example 16
  • Example 17 Example 18 Anode and Cathode Coating Material Electrically conductive Diamond Substrate Material Electrically conductive Silicon Diamond Layer Thickness ( ⁇ m) 10 10 10 10 10 10 Potential Window (V) 2.63 2.63 2.63 2.63 2.63 A/B 4.50 4.50 4.50 4.50 4.50 4.50 Conc. of Boron (ppm) 3000 3000 3000 3000 3000 Conc. of Sulfate Ion in Electrolyte (mol/l) 8.5 16.0 4.2 4.2 4.2 4.2 Conc.
  • Example 19 Example 20
  • Example 21 Example 22
  • Example 23 Example 24
  • Example 1 Compar.
  • Example 2 Compar.
  • Example 3 Compar.
  • Example 4 Compar.
  • Example 5 Anode and Cathode Coating Material Electrically conductive Diamond Carbon Substrate Material Electrically conductive Silicon - Diamond Layer Thickness ( ⁇ m) 10 10 0.8 26 - Potential Window (V) 1.97 3.90 1.99 3.60 1.90 A/B 2.00 7.20 1.49 6.30 - Conc. of Boron (ppm) 3000 3000 3000 3000 - Conc. of Sulfate Ion in Electrolyte (mol/l) 4.2 4.2 4.2 4.2 4.2 4.2 Conc.
  • Example 7 Example 8
  • Example 9 Example 10
  • Example 11 Example 12 Current Efficiency (%) 38 41 54 55 30 42 Conc. of Oxidizing Agent (mol/l) 0.79 0.85 1.12 1.14 0.62 0.87 Cell Voltage (V) 11.000 10.900 9.800 9.500 10.400 10.300 Durability ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇
  • Example 19 Example 20
  • Example 21 Example 22
  • Example 23 Example 24
  • Example 25 Current Efficiency (%) 46 49 54 55 97 34 53 Conc. of Oxidizing Agent (mol/l) 0.95 1.02 1.12 1.14 0.05 1.76 1.10 Cell Voltage (V) 6.400 7.902 13.200 15.000 10.200 10.200 10.300 Durability ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇
  • the diamond electrode by the present invention is effective to form oxidizing agent stably, in particular, when it is used as anode for the sulfuric acid electrolysis and the effect is further enhanced when it is used, at the same time, as cathode for the sulfuric acid electrolysis. Furthermore, the electrically conductive diamond electrode by the present invention can be used as anode and cathode for other electrolyses.

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EP11851375.3A 2010-12-21 2011-11-21 Elektrisch leitfähige diamantelektrode sowie schwefelsäure-elektrolyseverfahren und schwefelsäure-elektrolysevorrichtung damit Withdrawn EP2657370A4 (de)

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PCT/JP2011/076781 WO2012086352A1 (ja) 2010-12-21 2011-11-21 導電性ダイヤモンド電極、これを用いた、硫酸電解方法及び硫酸電解装置

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CN106917104A (zh) * 2017-03-17 2017-07-04 南开大学 一种用bdd电极电合成过硫酸盐的方法
JP2019044229A (ja) * 2017-09-01 2019-03-22 栗田工業株式会社 Ａｂｓ系樹脂表面のめっき前処理方法、ａｂｓ系樹脂表面のめっき処理方法、及びａｂｓ系樹脂めっき製品
JP6947783B2 (ja) * 2017-09-01 2021-10-13 栗田工業株式会社 Ａｂｓ系樹脂表面のめっき前処理方法、及びａｂｓ系樹脂表面のめっき処理方法
JP6953484B2 (ja) * 2017-09-01 2021-10-27 栗田工業株式会社 Ａｂｓ系樹脂表面のめっき前処理方法、ａｂｓ系樹脂表面のめっき処理方法、及びａｂｓ系樹脂めっき製品
CN111020623A (zh) * 2019-12-31 2020-04-17 河北中科同创科技发展有限公司 一种密闭电解槽

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TW200738911A (en) * 2006-01-20 2007-10-16 Toyo Tanso Co Electrolytic apparatus for producing fluorine or nitrogen trifluoride
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JP4460590B2 (ja) * 2007-06-22 2010-05-12 ペルメレック電極株式会社 導電性ダイヤモンド電極構造体及びフッ素含有物質の電解合成方法
JP5320173B2 (ja) * 2008-06-30 2013-10-23 クロリンエンジニアズ株式会社 硫酸電解方法
JP5358303B2 (ja) * 2008-06-30 2013-12-04 クロリンエンジニアズ株式会社 電解硫酸による洗浄方法及び半導体装置の製造方法
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US10662538B2 (en) 2015-05-26 2020-05-26 Condias Gmbh Method for producing a diamond electrode and diamond electrode

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