201033408 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種在電化學反應中可用於基材之轉化 * 的電極，特別是用於氧化劑生成的電極。 ' 【先前技術】 ' 可在電化學反應中用於基材之轉化的已知氣體擴散型 Φ 電極需要特別的電極結構。此種氣體擴散型電極係由多孔 性材料組成，該多孔性材料係施加至電極或組成電極。若 欲將電化學方法在氣體擴散型電極上進行，則必須確保反 應氣體之流入及流出。 電極之通氣經描述於文獻中，其中此種通氣係在電解 電池外部發生。然而，若電解質在電解電池外部（例如在 接收槽中）通氣，則結果是在經管或管線的輸送期間，在 該等導管中分別發生氣體釋出及氣墊（gas cUsi〇ns)形成 φ 。此實質降低使電極通氣之優點。 令人驚訝地’現在已發現：可實際防止氣體釋出及氣 墊形成的可能性。 【發明內容】 在一方面，本發明提供一種電極，其特徵在於該電極 包含使電極室中的電解質通氣之裝置。 依本發明所提供之電極在此也稱爲“依本發明之電極 -5- 201033408 使電極室中的電解質通氣之裝置包含適於導入氣體（ 較佳是包含空氣及氧氣之氣體）的裝置。 較佳地，在依本發明之電極中提供數個適於導入氣體 之裝置。 適於將氣體導入依本發明之電極的電極室之裝置可以 有不同形式（例如蠟燭形狀），且包含例如入口管或通氣 用熔塊，較佳是通氣用熔塊，特佳是玻璃熔塊或由氟塑膠 (PTFE ' PFA ' FEP )製之熔塊。 在另一方面，本發明提供一種電極，例如依本發明之 電極，其特徵在於電極包含三維立體形式，例如柱狀體、 發泡體或纖維材料（例如氈製品）。 藉由堆疊電極材料，可以避免常包含複雜製造步驟之 特別電極結構。 在依本發明之電極室中的電極柱狀體係由導電性材料 組成。該材料可以是例如特別適於電化學反應且例如並較 佳地包含玻璃狀碳之材料。 導電性電極塡充材料應具有儘可能大的表面積，且因 此較佳以小顆粒形式存在。較佳地，顆粒是粒子，例如片 狀及球形的圓柱幾何形狀的顆粒，因爲彼係得自粒化方法 〇 依本發明之較佳的電極柱狀體包含粒化之玻璃狀碳。 藉由使用導電性發泡體或纖維材料（例如氈製品）作 爲電極材料，比表面積可以增加，且因此可以改良某些電 化學反應。 -6 - 201033408 依本發明之較佳的三維立體電極包含碳發泡體，彼也 稱爲“網狀玻璃碳發泡體”。 依本發明之較佳的三維立體電極包含碳之氈製品，其 ' 也稱爲“碳氈製品”。 在依本發明之電極中，使電極室中的電解質通氣的裝 * 置較佳被排列成使該電解質及該電極可以被通氣的形式。 若依本發明之電極包含電極柱狀體，則該裝置較佳被排列 φ 成使該電解質及該電極柱狀體之整個寬度及長度均可以被 通氣；通氣較佳由下往上進行（“下”及”上”意指依照重力 之下及上）。 依本發明之電極較佳存在於電解電池中。二電極室可 以藉由一間隔器分隔，或該電解電池可以呈開放電池形式 操作，亦即電極室無隔離。 含有依本發明之電極的電解電池可以例如用於基材之 電化學轉化。 ❿ 基材之電化學轉化（通氣對該基材是重要的）是常用 的技術，包含例如由氫氟酸製造氟，或代表由氧之不完全 還原之過氧化氫的生成或臭氧的電化學製造（陽極反應： H2〇 + 〇2-^ 〇3 + 2H + + 2e )。 依本發明之電極是較佳用於陰極反應之電極。 依本發明之電極較佳用於H2o2之製造，但不獨用於 此。此還原方法是基於2個電子之轉移且經由游離之H + 而獲得 H2〇2: 〇2 + 2H + + 2e·— H2〇2。 在還原期間所形成之H2〇2可以從含有依本發明之電 201033408 極的反應槽移除，且可以例如作爲氧化劑，或所形成之 H2〇2可以如所述地當場製造且直接在反應槽中使用且消 耗。 藉由依本發明之電極，在當場製造（例如在反應槽中 )之所形成的氧化劑的應用包含例如作爲漂白化學品的應 用、處理飮用水及工業用水的應用、消毒游泳池及渦流池 的應用、純化工業廢水之廢水下水道設施的應用、或降解 持久性物質的應用。 基於例示之具體實例更詳細說明本發明。 【實施方式】 實例1 1公升之具有3±0.1 pH値的0.05 M Na2S04溶液塡入 下述之實驗裝置中。經由軟管泵，該溶液從實驗室級反應 器，經恆溫器吸至電解電池中且返回該實驗室級反應器。 將20 A/m2之電流密度施加至陽極，溫度維持固定於25 °C φ ο 第一個試驗在無通氣電解質的情況下進行。在第二個 試驗中，電解質在0.5巴之過壓下於實驗室級反應器中用 20 Ι/h之空氣通氣，如文獻中所述。在第三個試驗中，電 解質直接在陰極空間中，經蠟燭狀氣體熔塊，在0.5巴過 壓下用20 Ι/h之空氣通氣。 圖1顯示所得結果之曲線圖，亦即所達到之過氧化氫 濃度對試驗時間之曲線圖；電解質：0.05 M Na2S04溶液 -8 - 201033408 :溫度：25°C ;通氣：空氣，20 l/h，0.5 度：20 A/m2 ; pH値：3 ;試驗體積：1公 合氧化物；陰極：背襯不鏽鋼之玻璃狀碳 藉由使陰極柱狀體通氣，陰極生成之 達成明顯可見的改良。與沒有任何通氣之 良變爲明顯，因過氧化氫濃度增加3 0%。 【圖式簡單說明】 圖1表示所達到之過氧化氫濃度對試 過壓；電流密 :陽極：銥混 狀體。 氧化氫的量可 驗相比，此改 時間之曲線圖 -9 -201033408 VI. Description of the Invention: [Technical Field] The present invention relates to an electrode which can be used for conversion of a substrate in an electrochemical reaction, particularly an electrode for oxidant formation. [Prior Art] A known gas diffusion type Φ electrode which can be used for the conversion of a substrate in an electrochemical reaction requires a special electrode structure. Such a gas diffusion type electrode is composed of a porous material which is applied to an electrode or a constituent electrode. If the electrochemical method is to be carried out on a gas diffusion type electrode, it is necessary to ensure the inflow and outflow of the reaction gas. Ventilation of electrodes is described in the literature where such venting occurs outside of the electrolytic cell. However, if the electrolyte is vented outside of the electrolysis cell (e.g., in the receiving tank), the result is that gas evolution and gas cushion formation φ occur in the conduits during transport through the tubes or lines. This substantially reduces the advantages of venting the electrodes. Surprisingly, it has now been found that the possibility of gas release and air cushion formation can be practically prevented. SUMMARY OF THE INVENTION In one aspect, the invention provides an electrode characterized in that the electrode comprises means for venting the electrolyte in the electrode compartment. The electrode according to the invention is also referred to herein as "electrode-5-201033408 according to the invention. The means for venting the electrolyte in the electrode compartment comprises means adapted to introduce a gas, preferably a gas comprising air and oxygen. Preferably, several means suitable for introducing a gas are provided in the electrode according to the invention. The means adapted to introduce a gas into the electrode compartment of the electrode according to the invention may have different forms (for example a candle shape) and comprise, for example, an inlet. a tube or a venting frit, preferably a venting frit, particularly a glass frit or a frit made of fluoroplastic (PTFE 'PFA 'FEP). In another aspect, the present invention provides an electrode, such as The electrode of the present invention is characterized in that the electrode comprises a three-dimensional form, such as a columnar body, a foam or a fibrous material (e.g., felt). By stacking the electrode material, a special electrode structure often comprising complicated manufacturing steps can be avoided. The electrode columnar system in the electrode compartment according to the invention consists of a conductive material. The material may for example be particularly suitable for electrochemical reactions and for example and preferably comprises glass. The material of the carbon-like material. The conductive electrode-filling material should have as large a surface area as possible, and thus is preferably present in the form of small particles. Preferably, the particles are particles, such as flaky and spherical cylindrical geometric particles, because The preferred electrode column according to the present invention comprises granulated glassy carbon. By using a conductive foam or a fiber material (for example, a felt) as an electrode material, the specific surface area can be Adding, and thus improving certain electrochemical reactions. -6 - 201033408 A preferred three-dimensional electrode according to the invention comprises a carbon foam, also referred to as a "reticulated glass carbon foam". A preferred three-dimensional electrode comprises a carbon felt article, also referred to as a "carbon felt article." In the electrode according to the invention, the means for venting the electrolyte in the electrode compartment are preferably arranged such that the electrolyte And the electrode may be in a ventilated form. If the electrode according to the present invention comprises an electrode column, the device is preferably arranged such that the entire width and length of the electrolyte and the electrode column are The ventilating is preferably carried out from the bottom to the top ("lower" and "upper" means according to gravity and above). The electrode according to the present invention is preferably present in the electrolytic cell. The two electrode chamber can be used by The spacers are separated, or the electrolytic cell can be operated in the form of an open cell, that is, the electrode chamber is not isolated. The electrolytic cell containing the electrode according to the invention can be used, for example, for electrochemical conversion of a substrate. Ventilation is important for the substrate) is a commonly used technique, including, for example, the production of fluorine from hydrofluoric acid, or the formation of hydrogen peroxide by incomplete reduction of oxygen or the electrochemical production of ozone (anode reaction: H2〇+ 〇2-^ 〇3 + 2H + + 2e ) The electrode according to the invention is preferably an electrode for cathodic reaction. The electrode according to the invention is preferably used for the manufacture of H2o2, but is not used exclusively for this purpose. This reduction method is based on the transfer of 2 electrons and obtains H2〇2 via free H + : 〇2 + 2H + + 2e·- H2〇2. The H2〇2 formed during the reduction may be removed from the reaction vessel containing the electric pole 201033408 according to the present invention, and may, for example, be used as an oxidizing agent, or the formed H2〇2 may be produced on the spot as described and directly in the reaction tank. Used and consumed. By the use of the electrode according to the invention, the application of the oxidant formed on the spot (for example in a reaction tank) comprises, for example, application as a bleaching chemical, application of treated hydrazine and industrial water, application of a sterilizing swimming pool and a vortex cell, The application of wastewater sewer facilities for the purification of industrial wastewater, or the application of degrading persistent substances. The invention will be described in more detail based on the specific examples illustrated. [Examples] Example 1 A 1 liter solution of 0.05 M Na2S04 having 3 ± 0.1 pH Torr was introduced into the experimental apparatus described below. The solution was pumped from the laboratory grade reactor through a thermostat to the electrolysis cell via a hose pump and returned to the laboratory grade reactor. A current density of 20 A/m2 was applied to the anode and the temperature was maintained at 25 °C φ. The first test was carried out without a venting electrolyte. In the second test, the electrolyte was vented in a laboratory-scale reactor at a pressure of 0.5 bar with 20 Torr/h of air as described in the literature. In the third test, the electrolyte was directly vented in the cathode space with a candle-like gas frit under a pressure of 0.5 bar and air with 20 Ι/h. Figure 1 shows a graph of the results obtained, that is, a graph of the hydrogen peroxide concentration reached for the test time; electrolyte: 0.05 M Na2S04 solution-8 - 201033408: temperature: 25 ° C; ventilation: air, 20 l / h , 0.5 degree: 20 A/m2; pH値: 3; test volume: 1 metric oxide; cathode: glassy carbon backed by stainless steel, by venting the cathode column, a significant improvement in cathode formation is achieved. It is obvious that there is no ventilation, and the concentration of hydrogen peroxide is increased by 30%. [Simple description of the diagram] Figure 1 shows the hydrogen peroxide concentration achieved by the test overpressure; current density: anode: 铱 mixed body. The amount of hydrogen peroxide is comparable to the curve of this change time -9 -