201111555 六、發明說明： 【發明所屬之技術領域】 本發明係有關於一種光電化學產氫反應器之光觸媒電極 及其製作方法，尤指涉及一種使用粉末狀光觸媒漿料構成之光 觸媒電極，特別係指可作為光電化學產氫反應器内之陽極者。 【先前技術】 目前尚在發展階段之水分解產氫用之光電化學反應器 ❿ （Photoelectr〇chemical Cell，PEC )主要有兩種構造，分別為一 單槽式（Single Cell或Undivided Cell )，即陰陽兩極室不分開； 另一則為雙槽或分離式（Double Cell或Divided Cell )，即陰陽 兩極室以適當之分隔物分離。其中，前者經常使用光觸媒懸浮 液來產生水分解作用，雖然操作簡單，但因其無法將水分解所 產生之氫氣及氧氣分開，不但操作危險，也無法有效利用所產 生之氫氣作為燃料。故一般常用犧牲試劑（Sacrificial Reagents)，如甲醇及亞硫酸鈉，來抑制氧氣之生成。惟，使 # 用犧牲試劑不僅浪費’亦會產生不當之副產品，因此依舊無法 有效使用於水分解以大量產氫之製程。至於後者則因能有效分 離氫氣及氧氣，故可安全操作，較適用於實際之產氫應用。因 此’使用雙槽式光電化學反應器來分解水以產製氫氣將是大勢 所趨。 一般雙槽式光電化學反應器須有一接受光照射之光觸媒 陽極（Photoanode)及一使用白金觸媒製作而不須接受光照射 之暗陰極（DarkCathode)。於酸性水溶液中，當光陽極觸媒， 如二氧化鈦（Ti〇2)，接受適當光源（hv)照射受激而產生電 201111555 子及電洞對（Electron/Hole Pair);電洞（h+ )可分解水分子產 生氧氣及氫離子，而電子（e·)經外環電路傳至暗陰極與氫離 子產生還原作用生成氫氣。其反應表示如下： 光觸媒受激：（Ti02)+2hv —2h++2e_ 光陽極反應：H20+2h+ —2H++l/202 暗陰極反應：2H++2e_->H2 全反應：（Ti02)+2hv+H20 — H2+l/202 由此可見光觸媒電極之作用主宰整個水分解產氫之反 應。因此’一製作良好之光觸媒電極對光電化學反應器之組成 而言係為最重要之一環。 按’光觸媒電極之製作有多種方法被研究開發，例如真空 濺鍍、陽極氧化及溶膠燒結等。目前主要係利用光觸媒溶膠 (Sol Gel)附著於金屬基材’如鈦金屬薄板，再於高溫下鍛燒 而成。然而，如第4圖所示，以上述溶膠燒結法所製之面積2 公分x2公分之改良可見光二氧化鈦光觸媒電極，於〇1M硫酸 水溶液中以Air Mass 1.5 (AM1.5)標準光源照射，並在常溫 下進行，以銀/氣化銀（Ag/AgCl)為參考電極，白金網對電極， 直線掃瞄速度為50毫伏/秒（mv/s)等實驗條件下，其所得之 光觸媒電極於有光（Light)電流曲線4及無光（Dark)電流 曲線5中可知，兩者之差值即為其光電流。由圖中可清楚測出 其光電流僅為G.3毫安培（mA)。可見其光觸_量低，且 水分解效果也不佳，故難以達職業應用之目標。而許多合成 為粉末狀㈣之光觸媒亦無法_此種方法製域電極。^， 一般習用者係無法符合使用者於實際使用時之所需。 201111555 【發明内容】 β、^發明之主要目的係在於’克服習知技藝所遭遇之上述問 j並&供種使用粉末狀光觸媒構成之光觸媒電極，並可作為 光電化學產氫反應器内之陽極者。 ，本發明之次要目的係在於，提供一種可將難以加工之粉末 狀光觸媒製作成可供光電化學產氫反應器使用之電極，並容易 調控電極觸媒層之組成，而可獲致良好之效能者。 為達以上之目的，本發明係一種光電化學產氫反應器之光 • 觸媒電極及其製作方法’係使用粉末狀光觸媒構成之電極而可 作為產氫反應器内之陽極者，其包括一碳質電極基材及一披覆 於該碳質電極基材上之光觸媒層所構成。其中，該光觸媒層係 以粉末狀光觸媒、離子連結劑及導電性碳粉混合之漿料為構成 者’藉以均勻塗伸於該碳質電極基材上以構成之。 【實施方式】 请參閱『第1圖及第2圖』所示，係分別為本發明之結構 鲁 示思圖及本發明之流程示意圖。如圖所示：本發明係一種使用 粉末狀光觸媒之光電化學產氫反應器之光觸媒電極及其製作 方法’係適用於光電化學產氫反應器内之陽極，其包括一碳質 電極基材11及一披覆於該碳質電極基材11上之光觸媒層 1 2所構成，係可有效解決使用粉末狀光觸媒不易加工製作電 極之難題，並且容易調控電極觸媒之組成。 上述碳質電極基材1 1係為一碳布（Carbon Cloth)或無 觸媒氣體擴散電極（Non-catalyzed Gas Diffusion Electrode)。 而披覆於該碳質電極基材1 1上之光觸媒層1 2，係以粉末狀 201111555 光觸媒、離子連結劑及導電性碳粉混合之漿料為構成者，其中 該粉末狀光觸媒與該導電性碳粉之比例範圍並不設限，可為多 種，並以5:1為最佳者。以上所述，係構成一全新使用粉末狀 光觸媒之光電化學產氫反應器之光觸媒電極1。 上述光觸媒電極1係適用於水分解產氫之光電化學反應 器之陽極，其製作流程如第2圖所示，至少包括下列步驟： (A )將一粉末狀光觸媒1 11與一離子連結劑1 12及 一導電性碳粉113置一容器中混合，經超音波振盪數分鐘， 再攪拌調製成一均勻混合之光觸媒漿料，其中該離子連結劑工 1 2係為含離子交換劑（i〇nomer)之全氟聚苯乙烯磺酸 (Nafion)溶液，且該粉末狀光觸媒1 1 1係為可見光觸媒 (Visible Light-Driven Photo-catalysts)，如飢酸纽（BiV04)、 及紫外線光觸媒（VU-Responsive Photo-catalysts)，如二氧化 鈦（Ti〇2)，而該導電性碳粉1 1 3係為一傳統性之導電性碳 黑，如Vulcan XC72碳黑及單管（Single-Walled)或多管 (Multi-Walled Carbon Nanotube)之奈米碳管； (B )將上述調配好之光觸媒漿料均勻塗佈於一碳質電極 基材1 1，使光電極觸媒完全披覆於該碳質電極基材i i上而 形成一光觸媒層12;以及 (C)將上述光觸媒層12整平乾燥，即構成一光觸媒電 極1。 上述即為本發明使用粉末狀光觸媒，經由簡易之觸媒漿料 塗佈法獲付之光觸媒電極，並可使用各種適當之粉末狀光觸 媒’作為光電化學產氮反應器内之陽極。 當本發明於配製時，於一較佳實施例中，係使用商用二氧 201111555 化鈦（Degussa P25)光觸媒構成之電極，作為光電化學產氫 反應器之陽極，其步驟包含： (A 1 )將一 1〇〇毫克DegUSSa P25二氧化鈦光觸媒，與 一 〇_5毫升且濃度為20%之Nafion溶液，及一 20毫克vu〖can XC72導電性碳粉，置於一小燒杯中混合，經超音波振盪約$ 分鐘及手動攪拌約1〇,分鐘，調製成一均勻混合之光觸媒漿料； (B 1 )將一未經疏水處理過之碳布（Eleetr〇Chem， EC-CC1-060)作為電極基材，以大小為2公分χ2公分之方形，’ • 置於一玻璃平板上，再將上述調配好之光觸媒漿料均勻塗佈於 該電極基材上，使光電極觸媒完全披覆於該電極基材上而形成 一光觸媒層；以及 (C 1 )將上述塗佈有該光觸媒層之電極基材覆以一聚氣 乙烯塑膠（Polyvinyl Chloride，PVC)薄膜’並以一平板壓力機 於常溫下，施以10大氣壓力加壓處理2〇分鐘，使該光觸媒層 平滑均勻後’再將此覆有光觸媒層之電極基材置於空氣中乾燥 3天，即構成一光觸媒電極。 籲 為證實本發明所製作之光觸媒電極係可產生極高之光電 流’適合作為光電化學產氫反應器使用之陽極，故於0.1M硫 酸水溶液中以Air Mass 1.5 (AM1.5)標準光源照射，並在常 溫下進行，以銀/氯化銀（Ag/AgC1)為參考電極，白金網對電 極，直線掃瞒速度為50毫伏/秒（mV/s)。請參閱『第3圖』 所示’係本發明光觸媒電極於有光及無光照射下之陽極電流曲 線示意圖。如圖所示：經由本發明光觸媒電極於有光（Light) 電流曲線2及無光（Dark)電流曲線3中可知，兩者之差值即 為其光電流。當電壓大於1.05 V (Ag/AgCl)時，開始產生光 201111555 電流’而於1.5 V(Ag/Aga)以上時，其光電流達到穩定狀態。 由圖中左上角插入圖可清楚測出光電流約為2 5毫安培(爪八)。 與.習知技術所製相同面積之二氧化鈦光觸媒電極在相同 實驗條件下作比較（請參第4騎示），可清楚得知習知技術 測出之光f麟0.3亳安培，僅約為本發明所料電極者之 8 了見本發明製作之光觸媒電極係具有極佳之產生光電流 效能’足罐縣發狀電極粉作為光電辦錢反應器内 之1¼極所使用。 此外，當維持離子連結劑（20%Naflon溶液）之含量不變 而改變光觸媒與導電性碳粉比例，可發現所製作之光觸媒電極 產生之光電流亦隨之改變。而兩者重量以5:1之比例所產生之 光電机為最佳。-般而言，本發明製作之電極其細媒用量係 可隨易調整，且採用之光觸媒亦可使用任何粉末狀者，經離子 連結劑結合之光電極觸媒層其結構亦呈多孔性大面積狀態，故 能比他法所製作之光觸媒電極產生較高之光電流。 綜上所述，本發明係-種光電化學產氫反應器之細媒電 極及其製作方法，可有效改善習用之種種缺點，係可將難以加 工之粉末狀細媒製作成可供光電化學產氫反應器使用之電 極，並容易調控光電極觸媒層（组成，以€致良好之效能者， 進而使本發明之産生能更進步、更實用、更符合使用者之所 須’確已符合發明專利申請之要件’爰依法提出專利申請。 惟以上所述者’僅為本發明之較佳實施例而已，當不能以 此限定本㈣實施之範圍；故，凡依本發明巾請專利範圍及發 明說明書内容所作之解的等效變化與修飾，皆應仍屬本發明 專利涵蓋之範圍内。 201111555 【圖式簡單說明】 第1圖，係本發明之結構示意圖。 第2圖，係本發明之流程示意圖。 第3圖，係本發明光觸媒電極於有光及無光照射下之陽極 電流曲線示意圖。 μ 光照射下之陽極電 第4圖，係習用光觸媒電極於有光及無 流曲線示意圖。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photocatalyst electrode for a photoelectrochemical hydrogen production reactor and a method for fabricating the same, and more particularly to a photocatalyst electrode formed using a powder photocatalyst slurry, in particular Refers to the anode in the photoelectrochemical hydrogen production reactor. [Prior Art] Photoelectr〇chemical Cell (PEC), which is currently in the development stage of water decomposition, has two main structures, one single cell (Single Cell or Undivided Cell), ie The yin and yang chambers are not separated; the other is double-cell or separate (Double Cell or Divided Cell), that is, the yin and yang chambers are separated by appropriate partitions. Among them, the former often uses a photocatalyst suspension to generate water decomposition. Although the operation is simple, since it cannot separate the hydrogen and oxygen generated by the decomposition of water, it is not only dangerous to operate, but also cannot effectively utilize the generated hydrogen as a fuel. Therefore, Sacrificial Reagents such as methanol and sodium sulfite are commonly used to suppress the formation of oxygen. However, the use of sacrificial reagents is not only wasteful, but also produces improper by-products, so it is still not effectively used in the process of water decomposition to produce hydrogen in large quantities. As for the latter, it can be safely separated because it can effectively separate hydrogen and oxygen, and is more suitable for practical hydrogen production applications. Therefore, it is a general trend to use a two-tank photoelectrochemical reactor to decompose water to produce hydrogen. In general, a two-tank photoelectrochemical reactor must have a photocatalyst (Photoanode) that is exposed to light and a dark cathode (DarkCathode) that is made of platinum catalyst without being exposed to light. In an acidic aqueous solution, when a photoanode catalyst, such as titanium dioxide (Ti〇2), is excited by a suitable light source (hv) to generate electricity 201111555 and a pair of holes (Electron/Hole Pair); the hole (h+) can be The decomposition of water molecules produces oxygen and hydrogen ions, and the electrons (e·) are transmitted to the dark cathode via the outer loop circuit and the hydrogen ions are reduced to generate hydrogen. The reaction is expressed as follows: Photocatalyst is excited: (Ti02) + 2hv - 2h + 2e_ Photoanode reaction: H20 + 2h + - 2H + + l / 202 Dark cathode reaction: 2H + 2e_- > H2 Total reaction: (Ti02 ) +2hv+H20 — H2+l/202 The action of the visible light catalyst electrode dominates the reaction of hydrogen production by decomposition of the entire water. Therefore, a well-made photocatalyst electrode is one of the most important rings for the composition of a photoelectrochemical reactor. Various methods have been developed for the fabrication of photocatalyst electrodes, such as vacuum sputtering, anodizing, and sol sintering. At present, it is mainly deposited by a photocatalyst sol (Sol Gel) on a metal substrate such as a titanium metal sheet, and then calcined at a high temperature. However, as shown in Fig. 4, the modified visible light titanium dioxide photocatalyst electrode having an area of 2 cm x 2 cm prepared by the above sol sintering method is irradiated with an Air Mass 1.5 (AM 1.5) standard light source in a 1 M sulfuric acid aqueous solution, and Conducted at room temperature, with silver/vaporized silver (Ag/AgCl) as the reference electrode, platinum grid electrode, linear scanning speed of 50 mV / s (mv / s) and other experimental conditions, the resulting photocatalyst electrode It can be seen from the light current curve 4 and the dark current curve 5 that the difference between the two is its photocurrent. It can be clearly seen from the figure that its photocurrent is only G.3 milliamperes (mA). It can be seen that the amount of light contact is low, and the water decomposition effect is not good, so it is difficult to achieve the goal of occupational application. Many photocatalysts that are synthesized in powder form (4) are also unable to form a domain electrode. ^, the general practitioners are unable to meet the needs of the user in actual use. 201111555 [Summary content] The main purpose of the β, ^ invention is to overcome the above-mentioned problems encountered in the prior art and to provide a photocatalyst electrode composed of a powder photocatalyst, and can be used as a photoelectrochemical hydrogen production reactor. Anode. The secondary object of the present invention is to provide an electrode capable of processing a powder photocatalyst which is difficult to process into a photoelectrochemical hydrogen production reactor, and to easily adjust the composition of the electrode catalyst layer, thereby achieving good performance. By. For the purpose of the above, the present invention is a photocatalytic hydrogen generating reactor optical photocatalyst electrode and a method for fabricating the same, which is an electrode formed by a powder photocatalyst and can be used as an anode in a hydrogen generating reactor, which comprises a A carbonaceous electrode substrate and a photocatalyst layer coated on the carbonaceous electrode substrate. Here, the photocatalyst layer is formed by uniformly coating a carbonaceous electrode substrate with a slurry in which a powder photocatalyst, an ion coupling agent, and a conductive carbon powder are mixed. [Embodiment] Please refer to the "Fig. 1 and Fig. 2" diagrams, which are schematic diagrams of the structure of the present invention and the flow chart of the present invention. As shown in the figure, the present invention is a photocatalyst electrode for photoelectrochemical hydrogen production reactor using a powder photocatalyst and a method for fabricating the same, which is suitable for use in an anode in a photoelectrochemical hydrogen production reactor, comprising a carbonaceous electrode substrate 11 And a photocatalyst layer 12 coated on the carbonaceous electrode substrate 11 can effectively solve the problem that the electrode is not easily processed by using a powder photocatalyst, and the composition of the electrode catalyst can be easily regulated. The carbonaceous electrode substrate 11 is a carbon cloth or a non-catalyzed gas diffusion electrode (Non-catalyzed Gas Diffusion Electrode). The photocatalyst layer 12 coated on the carbonaceous electrode substrate 11 is composed of a slurry of a powdery 201111555 photocatalyst, an ion coupling agent and a conductive carbon powder, wherein the powder photocatalyst and the conductive material The proportion of the toner is not limited, it can be a variety of, and 5:1 is the best. As described above, a photocatalyst electrode 1 of a photoelectrochemical hydrogen production reactor using a powdery photocatalyst is constructed. The photocatalyst electrode 1 is suitable for the anode of a photoelectrochemical reactor for hydrolyzing hydrogen production, and the manufacturing process thereof is as shown in FIG. 2, and includes at least the following steps: (A) a powder photocatalyst 1 11 and an ion bonding agent 1 12 and a conductive carbon powder 113 are mixed in a container, ultrasonically oscillated for several minutes, and then stirred to prepare a uniformly mixed photocatalyst slurry, wherein the ion-bonding agent 12 is an ion-containing exchanger (i〇nomer) a perfluoropolystyrene sulfonic acid (Nafion) solution, and the powder photocatalyst 11 1 is a visible light-catalyst (Visible Light-Driven Photo-catalysts), such as hunt-dosing (BiV04), and ultraviolet photocatalyst (VU- Responsive Photo-catalysts), such as titanium dioxide (Ti〇2), and the conductive carbon powder 1 13 is a conventional conductive carbon black, such as Vulcan XC72 carbon black and single-tube (Single-Walled) or multi-tube (Multi-Walled Carbon Nanotube) carbon nanotubes; (B) uniformly coating the prepared photocatalyst slurry on a carbonaceous electrode substrate 1 1 so that the photoelectrode catalyst completely covers the carbonaceous electrode Forming a photocatalyst layer 12 on the substrate ii; And (C) flattening the photocatalyst layer 12 to form a photocatalyst electrode 1. The above is the photocatalyst electrode which is obtained by a simple catalyst slurry coating method using a powder photocatalyst according to the present invention, and various appropriate powder photocatalysts can be used as the anode in the photoelectrochemical nitrogen generating reactor. When the present invention is formulated, in a preferred embodiment, an electrode composed of a commercial photodiode 201111555 titanium (Degussa P25) photocatalyst is used as the anode of the photoelectrochemical hydrogen production reactor, and the steps thereof include: (A 1 ) One to one milligram of DegUSSa P25 titanium dioxide photocatalyst, one 〇5 ml of a 20% Nafion solution, and one 20 mg of vu〗 〖XC72 conductive carbon powder, mixed in a small beaker, supersonic Shake for about $ minutes and manually stir for about 1 〇, minutes to prepare a uniformly mixed photocatalyst slurry; (B 1 ) use a non-hydrophobic treated carbon cloth (Eleetr〇Chem, EC-CC1-060) as the electrode base Material, in a size of 2 cm χ 2 cm square, ' • placed on a glass plate, and then uniformly coated the photocatalyst slurry on the electrode substrate, so that the photoelectrode catalyst completely covers the material Forming a photocatalyst layer on the electrode substrate; and (C1) coating the electrode substrate coated with the photocatalyst layer with a polyvinyl chloride (PVC) film and using a flat plate press at room temperature Under, give 10 atmosphere Force pressing treatment 2〇 minutes, so that the photocatalyst layer was smooth and uniform 'and then coated with a photocatalyst layer of this electrode substrate was dried in air for 3 days constitute a photocatalyst electrode. In order to confirm that the photocatalyst electrode fabricated by the present invention can generate extremely high photocurrent 'suitable as an anode for photoelectrochemical hydrogen production reactor, it is irradiated with a standard light source of Air Mass 1.5 (AM 1.5) in a 0.1 M aqueous sulfuric acid solution, and It was carried out at room temperature with silver/silver chloride (Ag/AgC1) as the reference electrode and platinum platinum counter electrode with a linear broom speed of 50 mV/s (mV/s). Referring to Figure 3, there is shown a schematic diagram of the anode current curve of the photocatalyst electrode of the present invention in the presence of light and no light. As shown in the figure, it is known from the photocatalytic electrode of the present invention that there is a light current curve 2 and a dark current curve 3, and the difference between the two is its photocurrent. When the voltage is greater than 1.05 V (Ag/AgCl), the light starts to generate light at 201111555 and above 1.5 V (Ag/Aga), the photocurrent reaches a steady state. It can be clearly seen from the upper left corner of the figure that the photocurrent is about 25 mA (claw eight). Comparing with the same area of titanium dioxide photocatalyst electrode made by the conventional technology under the same experimental conditions (please refer to the fourth riding), it can be clearly known that the light measured by the conventional technology is 0.3 amps, only about this According to the invention, the photocatalyst electrode system produced by the invention has excellent photocurrent performance. The foot can be used as the 11⁄4 pole in the photovoltaic money reactor. In addition, when the content of the photocatalyst and the conductive toner was changed while maintaining the content of the ionic bonding agent (20% Naflon solution), it was found that the photocurrent generated by the photocatalyst electrode was also changed. The optical motor produced by the ratio of 5:1 is the best. In general, the amount of the fine medium used in the electrode of the present invention can be easily adjusted, and the photocatalyst used can also use any powder. The photoelectrode catalyst layer combined by the ion bonding agent is also porous. The area state, so it can produce higher photocurrent than the photocatalyst electrode made by other methods. In summary, the present invention is a thin-electrode electrode for a photoelectrochemical hydrogen-producing reactor and a manufacturing method thereof, which can effectively improve various disadvantages of the conventional use, and can prepare a powdery fine medium which is difficult to process into a photoelectrochemical product. The electrode used in the hydrogen reactor, and it is easy to regulate the photoelectrode catalyst layer (to make it better, so that the production of the invention can be more advanced, more practical, more in line with the user's needs) The patent application for the invention patent application is filed in accordance with the law. However, the above description is only a preferred embodiment of the present invention, and the scope of the implementation of the present invention cannot be limited thereto; The equivalent changes and modifications of the solutions made by the contents of the description of the invention are still within the scope of the invention. 201111555 [Simplified description of the drawings] Fig. 1 is a schematic view of the structure of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 3 is a schematic diagram showing the anode current curve of the photocatalyst electrode of the present invention in the presence of light and no light. The fourth embodiment of the anode electricity under the irradiation of light is used. The photocatalyst electrode is schematically represented by a light and no flow curve.
【主要元件符號說明】 (本發明部分） 光觸媒電極1 碳質電極基材11 粉末狀光觸媒111 離子連結劑112 導電性碳粉113 光觸媒層1 2 有光電流曲線2 無光電流曲線3 (習用部分） 有光電流曲線4 無光電流曲線5[Description of main components] (Part of the invention) Photocatalyst electrode 1 Carbonaceous electrode substrate 11 Powder photocatalyst 111 Ion bonding agent 112 Conductive carbon powder 113 Photocatalyst layer 1 2 Photocurrent curve 2 No photocurrent curve 3 (Used part) ) Photocurrent curve 4 No photocurrent curve 5