JP2009052095A - Method for activating electroconductive diamond electrode, and electrolysis method with the use of activated electrode - Google Patents
Method for activating electroconductive diamond electrode, and electrolysis method with the use of activated electrode Download PDFInfo
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- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 109
- 239000010432 diamond Substances 0.000 title claims abstract description 109
- 238000000034 method Methods 0.000 title claims abstract description 52
- 230000003213 activating effect Effects 0.000 title claims abstract description 9
- 238000005868 electrolysis reaction Methods 0.000 title claims description 30
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 27
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- 229910052786 argon Inorganic materials 0.000 claims abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- 239000000758 substrate Substances 0.000 claims description 19
- 230000005284 excitation Effects 0.000 claims description 16
- 230000004913 activation Effects 0.000 claims description 12
- 150000002431 hydrogen Chemical class 0.000 claims description 10
- 238000003682 fluorination reaction Methods 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000004020 conductor Substances 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 238000004050 hot filament vapor deposition Methods 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 230000001678 irradiating effect Effects 0.000 claims 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 28
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 238000005229 chemical vapour deposition Methods 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 15
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 12
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 11
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 10
- 238000001994 activation Methods 0.000 description 10
- 229910052731 fluorine Inorganic materials 0.000 description 10
- 239000011737 fluorine Substances 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 8
- -1 fluoride ions Chemical class 0.000 description 7
- 239000011698 potassium fluoride Substances 0.000 description 7
- 238000001069 Raman spectroscopy Methods 0.000 description 6
- 230000010287 polarization Effects 0.000 description 6
- 238000004611 spectroscopical analysis Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000000977 initiatory effect Effects 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000005283 ground state Effects 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 230000000717 retained effect Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- 229910017855 NH 4 F Inorganic materials 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- WXRGABKACDFXMG-UHFFFAOYSA-N trimethylborane Chemical compound CB(C)C WXRGABKACDFXMG-UHFFFAOYSA-N 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- QKCGXXHCELUCKW-UHFFFAOYSA-N n-[4-[4-(dinaphthalen-2-ylamino)phenyl]phenyl]-n-naphthalen-2-ylnaphthalen-2-amine Chemical compound C1=CC=CC2=CC(N(C=3C=CC(=CC=3)C=3C=CC(=CC=3)N(C=3C=C4C=CC=CC4=CC=3)C=3C=C4C=CC=CC4=CC=3)C3=CC4=CC=CC=C4C=C3)=CC=C21 QKCGXXHCELUCKW-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Physical Vapour Deposition (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
Description
本発明は、導電性ダイヤモンド電極の賦活化方法と当該方法により賦活化された導電性ダイヤモンドを使用する電解方法に関する。 The present invention relates to a method for activating a conductive diamond electrode and an electrolysis method using conductive diamond activated by the method.
従来より、フッ素ガスやフッ素化合物を合成する方法として、電解浴に無水フッ化水素(ＨＦ)、或いはＨＦを含む混合溶融塩を用いた電解フッ素化方法が知られている。
フッ化カリウム(ＫＦ)とＨＦのモル比が１：２であるＫＦ・ＨＦ混合溶融塩を電解浴として用いる方法が、フッ素ガスの合成に工業的に実用されている。
フッ化アンモニウム(ＮＨ4Ｆ)とＨＦのモル比が１：（１〜3）であるＮＨ4Ｆ・ＨＦ混合溶融塩を電解浴として用いる方法が、三フッ化窒素ガスの合成方法として、工業的に実用されている。
Conventionally, as a method of synthesizing fluorine gas or a fluorine compound, an electrolytic fluorination method using anhydrous hydrogen fluoride (HF) or a mixed molten salt containing HF in an electrolytic bath is known.
A method of using, as an electrolytic bath, a KF / HF mixed molten salt having a molar ratio of potassium fluoride (KF) and HF of 1: 2 is practically used for the synthesis of fluorine gas.
As a method for synthesizing nitrogen trifluoride gas, a method of using NH 4 F / HF mixed molten salt having a molar ratio of ammonium fluoride (NH 4 F) and HF of 1: (1-3) as an electrolytic bath is an industrial method. Practically used.
電解浴として、ＨＦに有機化合物を溶かしたものを用い、該有機物を電解フッ素化する方法もシモンズ法として知られ、工業的に採用されている。
フッ素ガスの製造に用いられていると同様のＫＦ・２ＨＦを電解浴に用い、陽極内部の底側から上側へ向かってガス状の有機化合物を流すことにより、該有機化合物をフッ素化する方法もフィリップ法として、よく知られた方法である。
これらの電解フッ素化方法において、陽極には、グラファイトなどの炭素質材料やニッケルが用いられている。炭素質材料においては、該炭素質が発生したフッ素ガスと反応して、フッ化グラファイトが生成し、これが電解の継続を阻害する(陽極効果)といった問題が、更にニッケルにおいては電極材料であるニッケルが電解浴に溶解して多量のスラッジを発生させるといった問題が、今なお存在する。
As an electrolytic bath, a method in which an organic compound is dissolved in HF and the organic material is subjected to electrolytic fluorination is also known as the Simmons method and is industrially adopted.
There is also a method of fluorinating the organic compound by using the same KF · 2HF used in the production of fluorine gas for the electrolytic bath and flowing the gaseous organic compound from the bottom to the top inside the anode. This is a well-known method as the Philip method.
In these electrolytic fluorination methods, a carbonaceous material such as graphite or nickel is used for the anode. Carbonaceous materials react with the fluorine gas generated by the carbonaceous material to produce graphite fluoride, which hinders the continuation of electrolysis (anodic effect). However, there still exists a problem that a large amount of sludge is generated by dissolving in an electrolytic bath.
これら陽極材料に関わる問題点を解決する方法として、半導体、または導電性ダイヤモンド膜を陽極材料として用いる方法、即ち導電性ダイヤモンド電極が提案されている。
前記特許文献はいずれも、半導体、または導電性ダイヤモンド電極の作成方法として、シリコンや炭素材料などの基体にダイヤモンド膜を成膜する方法を開示しており、ダイヤモンド膜を成膜する方法としてＣＶＤ(化学蒸着)法を開示している。
電解フッ素化合物の合成を目的とする電解槽においては、効率的に反応を進行させる目的や、電解槽を小型化する目的のために、一つの電解槽内に板状、または棒状の複数の陽極、及び陰極を交互に配置することが一般的である。また、陽極生成物と陰極生成物を区分するために、陽極と陰極の間に隔壁(スカート)を設置することが一般的である。該電解槽構造においては、陽極と陰極が互いに対向するため、陽極、陰極のいずれも、板状の場合にはその両面が、棒状の場合にはその全周が、電極活性を有する必要がある。
Each of the aforementioned patent documents discloses a method for forming a diamond film on a substrate such as silicon or carbon material as a method for producing a semiconductor or conductive diamond electrode, and CVD (as a method for forming a diamond film). Chemical vapor deposition) method is disclosed.
In an electrolytic cell for the purpose of synthesizing an electrolytic fluorine compound, a plurality of plate-shaped or rod-shaped anodes are used in one electrolytic cell for the purpose of efficiently proceeding the reaction or reducing the size of the electrolytic cell. In general, the cathodes are alternately arranged. In order to distinguish the anode product and the cathode product, it is common to install a partition (skirt) between the anode and the cathode. In the electrolytic cell structure, since the anode and the cathode face each other, both the anode and the cathode need to have electrode activity in the case of a plate shape, and the entire circumference in the case of a rod shape. .
一方、前記半導体、または導電性ダイヤモンド膜を成膜するＣＶＤ法では、ダイヤモンドの原料ガスは熱、或いはプラズマなどの励起部に供給され、励起されたガスは励起部に対向して設置された基体に供給される。該基体は、その背面に設置したヒーターで適切な温度に維持され、その基体の表面で成膜を進行させる。このため、板の両面に、あるいは棒の外周にダイヤモンドを成膜するためには、少なくとも２回以上の成膜操作が必要となる。
本発明者らは、板状の炭素質材料を基体として、その両面の表面に２回のＣＶＤ操作によって導電性ダイヤモンドを成膜した電解用電極を、フッ化物イオンを含有する電解浴を用いるフッ素含有物質の電解合成に供したところ、該電極の片面は合成に対して活性であるものの、他方の面は不活性であることを見出した。
On the other hand, in the CVD method for forming the semiconductor or conductive diamond film, the diamond source gas is supplied to an excitation part such as heat or plasma, and the excited gas is placed opposite to the excitation part. To be supplied. The substrate is maintained at an appropriate temperature by a heater installed on the back surface thereof, and film formation proceeds on the surface of the substrate. For this reason, in order to form a diamond film on both sides of the plate or on the outer periphery of the rod, at least two film forming operations are required.
The inventors of the present invention use a plate-like carbonaceous material as a base, an electrode for electrolysis in which conductive diamond is formed on the surfaces of both surfaces by two CVD operations, and fluorine using an electrolytic bath containing fluoride ions. When subjected to electrolytic synthesis of the contained material, it was found that one side of the electrode was active for synthesis but the other side was inactive.
本発明の目的は、その両面、または全周が、フッ化物イオンを含有する溶融塩電解浴を用いるフッ素含有物質の電解合成などの電解反応に利用することが可能な、炭素質材料を基体とする導電性ダイヤモンド電極の賦活化方法と、当該方法により賦活化された導電性ダイヤモンド電極を使用する電解方法を提供することにある。 An object of the present invention is to provide a carbonaceous material that can be used for an electrolytic reaction such as electrolytic synthesis of a fluorine-containing substance using a molten salt electrolytic bath containing fluoride ions on both sides or the entire circumference. It is an object of the present invention to provide a method for activating a conductive diamond electrode and an electrolytic method using the conductive diamond electrode activated by the method.
本発明は、炭素質材料から成る導電性材料を基体とし、その表面の少なくとも一部が導電性ダイヤモンドからなる電解用導電性ダイヤモンド電極の表面を、励起水素、励起酸素、及び励起アルゴンから選ばれる一種類以上と接触させることを特徴とする導電性ダイヤモンド電極の賦活処理方法であり、励起水素、励起酸素、及び励起アルゴン等との接触に代えて、前記導電性ダイヤモンド電極を、水溶液電解浴中で陽分極したり、化学酸化したりしても良い。更にこのように賦活化された導電性ダイヤモンド電極は電解フッ素化用に好ましく使用できる。 In the present invention, the surface of a conductive diamond electrode for electrolysis having a conductive material made of a carbonaceous material as a base and at least a part of the surface of which is made of conductive diamond is selected from excited hydrogen, excited oxygen, and excited argon. It is an activation treatment method for a conductive diamond electrode characterized by contacting with one or more kinds, and instead of contacting with excited hydrogen, excited oxygen, excited argon, etc., the conductive diamond electrode is placed in an aqueous electrolytic bath. It may be positively polarized or chemically oxidized. Furthermore, the conductive diamond electrode thus activated can be preferably used for electrolytic fluorination.
以下本発明を詳細に説明する。
本発明者らは、導電性ダイヤモンド電極に、励起した水素、励起した酸素、励起アルゴンを接触させること、特に照射することによって、或いは、該電極を水溶液中で陽分極することによって、あるいはまた、該電極の表面を化学酸化することによって、該電極を各種電解反応の電極として使用することを阻害する基体やダイヤモンド膜への損傷を生じさせることなく、析出した非ダイヤモンド構造の炭素質を除去できることを見出した。
The present invention will be described in detail below.
We contact the conductive diamond electrode with excited hydrogen, excited oxygen, excited argon, in particular by irradiation, or by anodic polarization of the electrode in an aqueous solution, or alternatively By chemically oxidizing the surface of the electrode, it is possible to remove the deposited non-diamond carbonaceous material without causing damage to the substrate or the diamond film that hinders the use of the electrode as an electrode for various electrolytic reactions. I found.
「励起」とは、基底状態以外の状態を意味し、基底状態のガスにエネルギを与えることにより、具体的には、プラズマ励起、或いは熱励起等により、励起状態に導くことができる。
本発明の賦活化処理を行うことによって、各種電解反応において、その全周、或いは両面を用いることのできる炭素質材料から成る導電性材料と基体とした導電性ダイヤモンド電極の提供が可能になる。
“Excitation” means a state other than the ground state, and can be led to an excited state by applying energy to the gas in the ground state, specifically, plasma excitation or thermal excitation.
By performing the activation treatment of the present invention, it is possible to provide a conductive diamond electrode using a conductive material composed of a carbonaceous material that can be used in the entire circumference or both sides in various electrolytic reactions and a substrate.
本発明の導電性ダイヤモンド電極、特にフッ化物イオンを含有する電解浴を用いたフッ素含有物質電解合成用陽極としての導電性ダイヤモンド電極では、その電極基体は、電解浴、及び電解生成物に対する耐食性の観点から、炭素質材料が好ましい。基体の形状は特に限定されず、板状、棒状、多孔性板状、パイプ状が使用できる。
基体表面上へのダイヤモンド膜の生成には、熱フィラメント法、マイクロ波プラズマ法、アークジェットプラズマ法などのＣＶＤ（化学蒸着）法や、ＰＶＤ（物理蒸着）法等を利用できる。
In the conductive diamond electrode of the present invention, particularly the conductive diamond electrode as the anode for electrolytic synthesis of fluorine-containing materials using an electrolytic bath containing fluoride ions, the electrode substrate has a corrosion resistance against the electrolytic bath and the electrolytic product. From the viewpoint, a carbonaceous material is preferable. The shape of the substrate is not particularly limited, and a plate shape, a rod shape, a porous plate shape, or a pipe shape can be used.
For the formation of the diamond film on the substrate surface, a CVD (chemical vapor deposition) method such as a hot filament method, a microwave plasma method, an arc jet plasma method, a PVD (physical vapor deposition) method, or the like can be used.
このように製造された導電性ダイヤモンド電極を、以下に述べる賦活化処理することによって、各種電解反応に好適に用いることができる。最も好ましい反応は、フッ化物イオンを含有する電解浴を用いた電解フッ素化反応であり、この他にも、食塩電解のような無機電解反応や、有機電解反応、電解水処理、電解めっきなどに使用できる。 The conductive diamond electrode thus produced can be suitably used for various electrolytic reactions by performing the activation treatment described below. The most preferable reaction is an electrolytic fluorination reaction using an electrolytic bath containing fluoride ions. In addition, for an inorganic electrolytic reaction such as salt electrolysis, an organic electrolytic reaction, electrolytic water treatment, electrolytic plating, etc. Can be used.
導電性ダイヤモンド電極の表面に、励起水素、励起酸素、励起アルゴンを接触させること、特に照射することによって賦活化が可能になるが、この方法では、ガスの励起と励起ガスを基体に照射（接触）できる装置であれば特に制限なく利用できるが、ダイヤモンドの成膜に利用したＣＶＤ装置の利用が好適である。該ＣＶＤ装置を利用する場合は、励起ガス照射時の装置条件は、ダイヤモンドの原料ガスの代わりに、水素、酸素、或いはアルゴンを用いる以外は、ダイヤモンドの成膜の条件と同様にすることが好ましい。励起ガス照射時間は特に限定されるものではないが、経済性の観点から１〜６０分であることが好ましい。 Activation can be achieved by bringing excited hydrogen, excited oxygen, and excited argon into contact with the surface of the conductive diamond electrode, particularly irradiation. In this method, the substrate is irradiated with gas excitation and excitation gas (contact). However, any CVD apparatus that can be used for diamond film formation is suitable. When using the CVD apparatus, it is preferable that the apparatus conditions at the time of excitation gas irradiation are the same as those for diamond film formation except that hydrogen, oxygen, or argon is used instead of the diamond source gas. . The excitation gas irradiation time is not particularly limited, but is preferably 1 to 60 minutes from the viewpoint of economy.
ダイヤモンドの成膜に利用したＣＶＤ装置を利用して賦活化処理する場合には、作製した導電性ダイヤモンド電極を一旦、ＣＶＤ装置から取り出した後に再度設置して処理することもできるが、装置から取り出すことなく、ダイヤモンドの成膜に引き続き、賦活化処理することもできる。 When the activation process is performed using the CVD apparatus used for forming the diamond film, the produced conductive diamond electrode can be once removed from the CVD apparatus and then installed again, but it can be removed from the apparatus. Therefore, the activation treatment can also be performed following the diamond film formation.
導電性ダイヤモンド電極を水溶液中で陽分極することによっても賦活化が可能である。この方法では、水溶液の種類は特に限定されず、酸性、アルカリ性、或いは中性の電解質を任意の濃度で含有する水溶液を使用することができる。該水溶液中に導電性ダイヤモンド電極の全部、或いは一部を浸漬して陽分極することで、浸漬した部分のダイヤモンド膜が賦活化される。
陽分極に要する電流密度、分極時間、温度は特に限定されるものではないが、基体に対する負荷を軽減するため、電流密度は０．１〜１０Ａ／ｄｍ2、分極時間は１〜１０分、温度は１０〜４０℃の範囲とすることが好ましい。
Activation can also be achieved by positively polarizing a conductive diamond electrode in an aqueous solution. In this method, the type of the aqueous solution is not particularly limited, and an aqueous solution containing an acidic, alkaline, or neutral electrolyte at an arbitrary concentration can be used. By immersing all or part of the conductive diamond electrode in the aqueous solution and anodic polarization, the immersed diamond film is activated.
The current density, polarization time, and temperature required for anodic polarization are not particularly limited, but in order to reduce the load on the substrate, the current density is 0.1 to 10 A / dm 2 , the polarization time is 1 to 10 minutes, and the temperature Is preferably in the range of 10 to 40 ° C.
賦活化は、導電性ダイヤモンド電極を化学酸化することによって行うことも可能である。この方法では、濃硝酸などの強酸化性溶液が使用でき、該酸化性溶液中に導電性ダイヤモンド電極の全部、或いは一部を浸漬することで、浸漬した部分のダイヤモンド膜が賦活化される。
溶液温度、浸漬時間は特に限定されるものではないが、電極基体に対する負荷を軽減するため、溶液温度は１０〜６０℃、浸漬時間は１〜６０分の範囲とすることが好ましい。
Activation can also be performed by chemically oxidizing a conductive diamond electrode. In this method, a strong oxidizing solution such as concentrated nitric acid can be used, and the immersed diamond film is activated by immersing all or part of the conductive diamond electrode in the oxidizing solution.
The solution temperature and the immersion time are not particularly limited, but in order to reduce the load on the electrode substrate, the solution temperature is preferably 10 to 60 ° C. and the immersion time is preferably in the range of 1 to 60 minutes.
これまで述べた賦活化は、導電性ダイヤモンド電極表面に、残存する非ダイヤモンド構造の炭素質を除去することが主たる目的であり、次に前記非ダイヤモンド構造の炭素質の生成及び除去に関して説明する。
以降、板状の炭素質材料を基体としてその両面に２回のＣＶＤ操作によって導電性ダイヤモンドを成膜した電解用電極に関して説明し、便宜的に、一度目のＣＶＤ操作でダイヤモンドを成膜する面をＡ面、２度目の操作で成膜する面をＢ面と称する。
The activation described so far is mainly intended to remove the carbonaceous material having a non-diamond structure remaining on the surface of the conductive diamond electrode. Next, generation and removal of the carbonaceous material having the non-diamond structure will be described.
Hereinafter, an electrode for electrolysis in which conductive diamond is formed on both surfaces of a plate-like carbonaceous material as a base by two CVD operations will be described. For convenience, the surface on which diamond is formed by the first CVD operation will be described. Is the A side, and the surface on which the film is formed by the second operation is referred to as the B side.
本発明者らの経験では、前記電極を、フッ化物イオンを含有する電解浴を用いたフッ素含有物質の電解合成に供すると、Ｂ面では反応が進行するものの、Ａ面では反応は進行しなかった。これを詳細に調査したところ、Ａ面の表面エネルギーが著しく低下しており、前記した炭素材料を陽極として、フッ化物イオンを含有する電解浴を用いてフッ素含有物質を電解合成する際に発生する陽極効果と同じ現象であった。
更には、２回のＣＶＤ操作を実施した直後の導電性ダイヤモンド電極の表面をラマン分光分析などで観察したところ、Ｂ面の主成分はダイヤモンドであったのに対し、Ａ面では、ダイヤモンド質の上部に非ダイヤモンド構造の炭素質が残存していることがわかった。
In the experience of the present inventors, when the electrode is subjected to electrolytic synthesis of a fluorine-containing substance using an electrolytic bath containing fluoride ions, the reaction proceeds on the B surface, but the reaction does not proceed on the A surface. It was. When this is investigated in detail, the surface energy of the A surface is remarkably reduced, and is generated when electrolytically synthesizing a fluorine-containing substance using the above-described carbon material as an anode and an electrolytic bath containing fluoride ions. It was the same phenomenon as the anode effect.
Furthermore, when the surface of the conductive diamond electrode immediately after the two CVD operations was observed by Raman spectroscopic analysis or the like, the main component of the B surface was diamond, whereas the A surface was diamond-like. It was found that the non-diamond carbonaceous material remained on the top.
ＣＶＤ法によるダイヤモンドの成膜過程において、基体表面では、１)ダイヤモンド膜の析出成長、２)非ダイヤモンド構造の炭素質の析出、及び３)励起ガスによる非ダイヤモンド構造の炭素質のエッチング、が競争的に起こっていると考えられている。原料ガスの励起や基体の温度などの諸条件を適切に維持できている場合には、前記１)の反応が充分速く、また、２)の反応よりも３)の反応が速いため、基体表面には、主としてダイヤモンド膜のみが成長する。一方、諸条件が適切に維持できていない場合には、２)の反応と比して充分速い１)の反応が得られない、或いは３)の反応が遅いなどの原因によって、非ダイヤモンド構造の炭素質が残存することとなる。 During the diamond film formation process by CVD, 1) diamond film deposition growth, 2) non-diamond carbonaceous deposition, and 3) non-diamond carbonaceous etching by excitation gas compete on the substrate surface. Is thought to be happening. When various conditions such as excitation of the source gas and substrate temperature are properly maintained, the reaction of 1) is sufficiently fast and the reaction of 3) is faster than the reaction of 2). Only the diamond film grows mainly. On the other hand, if the conditions are not properly maintained, the reaction of 1) is not sufficiently fast compared to the reaction of 2), or the reaction of 3) is slow. Carbonaceous matter will remain.
１回目のＣＶＤ成膜において、Ａ面はダイヤモンドが成長する条件下におかれるためにその表面にダイヤモンドが成長する。しかし、２回目のＣＶＤ成膜においては、Ｂ面にはダイヤモンドが成長するものの、Ａ面は励起ガスの供給部と対向しないなど、ダイヤモンドが成長する条件下ではないため、非ダイヤモンド構造の炭素質が析出したものと考えられる。
この様にＡ面には、非ダイヤモンド構造の炭素質が存在するために、これを、フッ化物イオンを含有する溶融塩中で陽極とした場合には、発生したフッ素ガスと反応して、電解反応が起こらない表面エネルギーの低いフッ化グラファイトが生成したと考えられる。
In the first CVD film formation, since the A surface is placed under the condition where diamond grows, diamond grows on the surface. However, in the second CVD film formation, diamond grows on the B surface, but the A surface does not face the excitation gas supply part, so that the diamond does not grow. Is considered to have precipitated.
In this way, since the non-diamond carbonaceous material is present on the A surface, when this is used as an anode in a molten salt containing fluoride ions, it reacts with the generated fluorine gas to cause electrolysis. It is thought that graphite fluoride having a low surface energy that does not cause a reaction was produced.
この非ダイヤモンド構造の炭素質を導電性ダイヤモンド電極表面から除去するために、本発明では、導電性ダイヤモンド電極を、励起水素、励起酸素、及び／又は励起アルゴンと接触させる。これにより励起ガスのエネルギが非ダイヤモンド構造の炭素質を電極表面から除去して自身は基底状態のガスに戻ると推測できる。 In order to remove this non-diamond carbonaceous material from the surface of the conductive diamond electrode, in the present invention, the conductive diamond electrode is brought into contact with excited hydrogen, excited oxygen, and / or excited argon. Thus, it can be assumed that the energy of the excitation gas removes the non-diamond carbonaceous material from the electrode surface and returns to the ground state gas.
本発明によると、励起水素、励起酸素、及び励起アルゴンから選ばれる一種類以上のガスを、非ダイヤモンド構造の炭素質をその表面に有する導電性ダイヤモンド電極の表面に接触させると、前記非ダイヤモンド構造の炭素質が除去されて、電極活性が高く維持される。 According to the present invention, when one or more gases selected from excited hydrogen, excited oxygen, and excited argon are brought into contact with the surface of a conductive diamond electrode having a non-diamond carbonaceous material on the surface thereof, the non-diamond structure The carbonaceous matter is removed, and the electrode activity is kept high.
次に本発明に係る導電性ダイヤモンド電極の賦活化方法、及び賦活化された電極を使用する電解反応の実施例及び比較例を記載するが、これらは本発明を限定するものではない。 Next, although the activation method of the electroconductive diamond electrode which concerns on this invention, and the Example and comparative example of the electrolytic reaction which use the activated electrode are described, these do not limit this invention.
［実施例１］
導電性基体として炭素板を使用し、該基体の両面を研磨、洗浄し、更にダイヤモンド粒子で核付けを行って熱フィラメントＣＶＤ装置に装着した。水素ガス中に１vol％のメタンガスと０．５ppmのトリメチルボロンガスを添加した原料ガスを、５リットル／分の速度で装置内に流しながら、装置内圧力を７５Torrに保持し、フィラメントに電力を印加して温度２４００℃に昇温した。このとき基体温度は８６０℃であった。８時間のＣＶＤ操作によって該基体の片面（Ａ面）にダイヤモンド膜を合成した後、同様のＣＶＤ操作によって、もう一方の面（Ｂ面）にダイヤモンド膜を合成し、両面を導電性ダイヤモンドで被覆した電極を作製した。
[Example 1]
A carbon plate was used as the conductive substrate, both surfaces of the substrate were polished and cleaned, and nucleated with diamond particles, and mounted on a hot filament CVD apparatus. While supplying a raw material gas with 1vol% methane gas and 0.5ppm trimethylboron gas in hydrogen gas flowing at a rate of 5 liters / minute, the internal pressure is maintained at 75 Torr and power is applied to the filament. The temperature was raised to 2400 ° C. At this time, the substrate temperature was 860 ° C. After synthesizing a diamond film on one side (A side) of the substrate by a CVD operation for 8 hours, a diamond film is synthesized on the other side (B side) by the same CVD operation, and both sides are coated with conductive diamond. An electrode was prepared.
作製した電極をＣＶＤ装置から取り出し、ラマン分光分析を行ったところ、Ａ面、Ｂ面ともにダイヤモンドに帰属する大きなピーク（１３３０cm-1付近）が検出され、その強度はほぼ同じであった。同様に、Ａ面、Ｂ面のいずれからも非ダイヤモンド構造の炭素質に帰属するピーク（１５８０ｃｍ-1付近）が検出されたが、その強度は、Ｂ面では小さかったのに対し、Ａ面では大きかった。
更に表面エネルギーを測定したところ、Ａ面は５０．５J／ｍ2、Ｂ面は５１．３J／ｍ2であった。
When the produced electrode was taken out from the CVD apparatus and subjected to Raman spectroscopic analysis, a large peak (around 1330 cm −1 ) attributed to diamond was detected on both the A and B faces, and the intensities thereof were almost the same. Similarly, A plane, a peak attributable to carbonaceous non-diamond structure from any B surface (1580 cm around -1) is detected and its intensity, while smaller in surface B, with A surface It was big.
Furthermore, when the surface energy was measured, the A side was 50.5 J / m 2 and the B side was 51.3 J / m 2 .
該電極を再び熱フィラメントＣＶＤ装置に取付け、原料ガスを水素ガスのみとしたこと以外はダイヤモンドの成膜と同様のＣＶＤ条件によって、励起水素を１０分間照射した。
ＣＶＤ装置から電極を取出し、ラマン分光分析を行ったところ、Ａ面の非ダイヤモンド構造炭素質帰属ピークが大きく減少し、Ａ面、Ｂ面のスペクトルはほぼ一致した。また、Ａ面、Ｂ面の表面エネルギーは、それぞれ４９．７J／ｍ2及び５１．０J／ｍ2であった。
The electrode was again attached to the hot filament CVD apparatus, and irradiated with excited hydrogen for 10 minutes under the same CVD conditions as for diamond film formation except that the source gas was only hydrogen gas.
When the electrode was taken out from the CVD apparatus and subjected to Raman spectroscopic analysis, the non-diamond structural carbonaceous assignment peak on the A plane was greatly reduced, and the spectra on the A and B planes almost coincided. Also, A plane, the surface energy of the B-side were respectively 49.7J / m 2 and 51.0J / m 2.
該電極を、建浴直後のＫＦ・２ＨＦ系溶融塩中に陽極として取付け、陰極にニッケル板を使用して電流密度１００Ａ／ｄｍ2で定電流電解を実施した。定電流電解中のダイヤモンド電極を観察したところ、Ａ面、Ｂ面からいずれからも気泡発生が認められた。電解２４時間後もＡ面、Ｂ面からの気泡発生が認められ、この時の槽電圧は７．９Ｖであった。電解２４時間後の該電極を、ＨＦで洗浄した後、Ａ面、Ｂ面の表面エネルギーを測定したところ、それぞれ３５．７J／ｍ2及び４０．２J／ｍ2であり、両面とも電解浴との濡れが保持される状態であることが確認された。 The electrode was mounted as an anode in a KF · 2HF molten salt immediately after building bath, and a constant current electrolysis was performed at a current density of 100 A / dm 2 using a nickel plate as the cathode. When the diamond electrode during constant current electrolysis was observed, bubble generation was observed from both the A and B surfaces. Even after 24 hours of electrolysis, bubbles were observed from the A and B surfaces, and the cell voltage at this time was 7.9V. The electrode 24 hours after initiation of the electrolysis, washed with HF, was measured the surface energy of the surface A, B plane, are each 35.7J / m 2 and 40.2J / m 2, and both surfaces electrolytic bath It was confirmed that the wettability was maintained.
[実施例２]
実施例1と全く同様の方法で、炭素板を基体とし、その両面を導電性ダイヤモンドで被覆した電極を作製した。２回のＣＶＤ操作によってＡ面及びＢ面にダイヤモンドを成膜したのに引き続き、該電極をＣＶＤ装置から取り出すことなく、メタンガス、トリメチルボロンガスを遮断して水素ガスのみ供給してＣＶＤ操作を３０分間継続した。
[Example 2]
In the same manner as in Example 1, an electrode having a carbon plate as a substrate and coated on both sides with conductive diamond was produced. After the diamond film is formed on the A and B surfaces by two CVD operations, the methane gas and trimethyl boron gas are cut off and only the hydrogen gas is supplied without removing the electrodes from the CVD apparatus. Continued for a minute.
該電極をＣＶＤ装置より取り出し、ラマン分光分析を行ったところ、Ａ面、Ｂ面のスペクトルはほぼ一致し、ダイヤモンドに帰属する大きなピーク（１３３０cm-1付近）と非ダイヤモンド構造の炭素質に帰属する小さなピーク（１５８０cm-1付近）が検出された。
Ａ面、Ｂ面の表面エネルギーはそれぞれ５０．１J／ｍ2、５０．３J／ｍ2であった。
When the electrode was taken out from the CVD apparatus and subjected to Raman spectroscopic analysis, the A-plane and B-plane spectra almost coincided with each other, and a large peak attributed to diamond (around 1330 cm −1 ) and a non-diamond carbonaceous substance were attributed. A small peak (near 1580 cm −1 ) was detected.
A surface, each surface energy of the B surface 50.1J / m 2, was 50.3J / m 2.
該電極を用いて、実施例1と同様の方法でＫＦ・２ＨＦ系溶融塩中で定電流電解を行ったところ、Ａ面、Ｂ面のいずれからも気泡発生が認められ、電解２４時間後の槽電圧は７．９Ｖであった。電解２４時間後の該電極を、ＨＦで洗浄した後に表面エネルギーを測定したところ、Ａ面、Ｂ面それぞれ２８．６J／ｍ2、３９．３J／ｍ2であり、両面とも電解浴との濡れが保持される状態であることが確認された。 Using this electrode, constant current electrolysis was performed in a KF · 2HF molten salt in the same manner as in Example 1. As a result, bubbles were observed from both the A side and B side, and 24 hours after the electrolysis. The cell voltage was 7.9V. Wetting the electrode 24 hours after initiation of the electrolysis was measured for a surface energy after washing with HF, A plane, B plane respectively 28.6J / m 2, was 39.3J / m 2, the both electrolytic bath Was confirmed to be in a state of being retained.
[実施例３]
実施例1と同様の方法で作製した導電性ダイヤモンド電極を、０．５mol／Lの過塩素酸水溶液に浸漬し、電流密度２Ａ／ｄｍ2で５分間陽分極した。この際、陰極にはジルコニウム板を使用した。
陽分極終了後、該電極を過塩素酸水溶液より取り出し、純水洗浄、及び乾燥した後にラマン分光分析したところ、Ａ面、Ｂ面のスペクトルはほぼ一致し、ダイヤモンドに帰属する大きなピーク（１３３０cm-1付近）と非ダイヤモンド構造の炭素質に帰属する小さなピーク（１５８０cm-1付近）が検出された。
Ａ面、Ｂ面の表面エネルギーはそれぞれ５７．２J／ｍ2、６５．３J／ｍ2であった。
[Example 3]
A conductive diamond electrode produced by the same method as in Example 1 was immersed in a 0.5 mol / L perchloric acid aqueous solution and positively polarized at a current density of 2 A / dm 2 for 5 minutes. At this time, a zirconium plate was used as the cathode.
After completion of the anodic polarization, the electrode was taken out from the perchloric acid aqueous solution, washed with pure water and dried, and then subjected to Raman spectroscopic analysis. As a result, the spectra of the A and B surfaces almost coincided, and a large peak (1330 cm − 1 ) and a small peak (near 1580 cm −1 ) attributed to the non-diamond carbonaceous material.
A surface, each surface energy of the B surface 57.2J / m 2, was 65.3J / m 2.
実施例1と同様の方法で、ＫＦ・２ＨＦ系溶融塩中で定電流電解を行った。定電流電解中のダイヤモンド電極を観察したところ、Ａ面、Ｂ面から気泡発生が認められた。電解２４時間後もＡ面、Ｂ面からの気泡発生が認められ、この時の槽電圧は７．９Ｖであった。電解２４時間後の該電極を、ＨＦで洗浄した後に表面エネルギーを測定したところ、Ａ面、Ｂ面それぞれ３５．７J／ｍ2、４０．２J／ｍ2であり、両面とも電解浴との濡れが保持される状態であることが確認された。 In the same manner as in Example 1, constant current electrolysis was performed in KF · 2HF molten salt. Observation of the diamond electrode during constant current electrolysis revealed that bubbles were generated from the A and B surfaces. Even after 24 hours of electrolysis, bubbles were observed from the A and B surfaces, and the cell voltage at this time was 7.9V. Wetting the electrode 24 hours after initiation of the electrolysis was measured for a surface energy after washing with HF, A plane, B plane respectively 35.7J / m 2, was 40.2J / m 2, the both electrolytic bath Was confirmed to be in a state of being retained.
[実施例４]
実施例1と同様の方法で作製した導電性ダイヤモンド電極を、１３．５mol／Lの硝酸水溶液に３分間浸漬した。純水洗浄、及び乾燥した後にラマン分光分析したところ、該電極のＡ面、Ｂ面のスペクトルはほぼ一致し、ダイヤモンドに帰属する大きなピーク（１３３０cm-1付近）と非ダイヤモンド構造の炭素質に帰属する小さなピーク（１５８０cm-1付近）が検出された。
Ａ面、Ｂ面の表面エネルギーはそれぞれ５９．４J／ｍ2、５８．７J／ｍ2であった。
[Example 4]
A conductive diamond electrode produced by the same method as in Example 1 was immersed in a 13.5 mol / L nitric acid aqueous solution for 3 minutes. When the Raman spectroscopic analysis was performed after washing with pure water and drying, the spectra of the A and B surfaces of the electrode were almost the same, and the large peak attributed to diamond (around 1330 cm -1 ) and the non-diamond carbonaceous attribute A small peak (around 1580 cm −1 ) was detected.
A surface, each surface energy of the B surface 59.4J / m 2, was 58.7J / m 2.
該電極を用いて、実施例1と同様の方法でＫＦ・２ＨＦ系溶融塩中で定電流電解を行ったところ、Ａ面、Ｂ面のいずれからも気泡発生が認められ、電解２４時間後の槽電圧は７．９Ｖであった。電解２４時間後の該電極を、ＨＦで洗浄した後に表面エネルギーを測定したところ、Ａ面、Ｂ面それぞれ２７．３J／ｍ2、３８．２J／ｍ2であり、両面とも電解浴との濡れが保持される状態であることが確認された。 Using this electrode, constant current electrolysis was performed in a KF · 2HF molten salt in the same manner as in Example 1. As a result, bubbles were observed from both the A side and B side, and 24 hours after the electrolysis. The cell voltage was 7.9V. Wetting the electrode 24 hours after initiation of the electrolysis was measured for a surface energy after washing with HF, A plane, B plane respectively 27.3J / m 2, was 38.2J / m 2, the both electrolytic bath Was confirmed to be in a state of being retained.
[比較例]
実施例1と同様の方法で作製した導電性ダイヤモンド電極を、そのまま、実施例1と同様の方法で、ＫＦ・２ＨＦ系溶融塩中で定電流電解を行った。定電流電解中の導電性ダイヤモンド電極を観察したところ、Ｂ面のダイヤモンド膜からの気泡発生は認められたが、Ａ面のダイヤモンド膜の表面はガスで被覆されており、連続的な気泡発生が認められなかった。
[Comparative example]
The conductive diamond electrode produced by the same method as in Example 1 was directly subjected to constant current electrolysis in a KF · 2HF molten salt by the same method as in Example 1. Observation of a conductive diamond electrode during constant-current electrolysis revealed that bubbles were generated from the B-side diamond film, but the surface of the A-side diamond film was covered with gas, and continuous bubble generation was observed. I was not able to admit.
電解２４時間後もＢ面のダイヤモンド膜のみから気泡発生が認められ、この時の槽電圧は８．１Ｖであった。電解２４時間後の陽極を、ＨＦで洗浄した後に表面エネルギーを測定したところ、Ａ面は７．７J／ｍ2、Ｂ面は４３．４J／ｍ2で，Ａ面の表面エネルギーは低く、電解浴との濡れ性が著しく低下していることが判った。Ａ面は所謂陽極効果が発生していた。 Even after 24 hours of electrolysis, bubbles were observed only from the B-side diamond film, and the cell voltage at this time was 8.1V. When the surface energy was measured after washing the anode with HF after 24 hours of electrolysis, the surface A was 7.7 J / m 2 and the surface B was 43.4 J / m 2. It was found that the wettability with the bath was significantly reduced. The so-called anode effect occurred on the A side.
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| JP2012092408A (en) * | 2010-10-28 | 2012-05-17 | Toyo Tanso Kk | Diamond-like carbon film and method for producing the same |
| JP2013100601A (en) * | 2011-10-14 | 2013-05-23 | I'msep Co Ltd | Surface modifying method by fluorination |
| JP2016152796A (en) * | 2010-01-31 | 2016-08-25 | 国立大学法人九州大学 | Animal and plant growth promotion methods |
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| JP2003206476A (en) * | 2002-01-10 | 2003-07-22 | Ishizuka Kenkyusho:Kk | Heat-treated diamond fine powder and method for producing the same |
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| JPH0648717A (en) * | 1992-07-24 | 1994-02-22 | Matsushita Electric Ind Co Ltd | Method for forming high-quality diamond |
| JP2003206476A (en) * | 2002-01-10 | 2003-07-22 | Ishizuka Kenkyusho:Kk | Heat-treated diamond fine powder and method for producing the same |
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| JP2016152796A (en) * | 2010-01-31 | 2016-08-25 | 国立大学法人九州大学 | Animal and plant growth promotion methods |
| JP2012092408A (en) * | 2010-10-28 | 2012-05-17 | Toyo Tanso Kk | Diamond-like carbon film and method for producing the same |
| JP2013100601A (en) * | 2011-10-14 | 2013-05-23 | I'msep Co Ltd | Surface modifying method by fluorination |
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