JP5664379B2 - Anode electrode for visible light decomposition of water and water visible light decomposition apparatus - Google Patents
Anode electrode for visible light decomposition of water and water visible light decomposition apparatus Download PDFInfo
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- JP5664379B2 JP5664379B2 JP2011061136A JP2011061136A JP5664379B2 JP 5664379 B2 JP5664379 B2 JP 5664379B2 JP 2011061136 A JP2011061136 A JP 2011061136A JP 2011061136 A JP2011061136 A JP 2011061136A JP 5664379 B2 JP5664379 B2 JP 5664379B2
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Description
本発明は、エネルギー分野や環境分野において水を酸素と水素に分解するために用いられる水の可視光分解用アノード電極に関する。 The present invention relates to an anode electrode for visible light decomposition of water used to decompose water into oxygen and hydrogen in the energy field and the environment field.
可視光で水を酸素と水素に分解することのできる電極は、これまでほとんど知られていなかったが、最近、ＴａＯＮ電極が水の可視光分解の光アノードとして動作することが報告された（非特許文献１）。しかし、このＴａＯＮ電極では、酸素発生に基づく光アノード電流を得るために、−０．０Ｖ ｖｓ Ａｇ／ＡｇＣｌのバイアスが必要であり、利用できる可視光も５４０ｎｍ以下に限定されていた。 Until now, few electrodes have been known that can decompose water into oxygen and hydrogen with visible light, but recently it has been reported that a TaON electrode acts as a photoanode for visible light decomposition of water (non- Patent Document 1). However, this TaON electrode requires a bias of −0.0 V vs Ag / AgCl in order to obtain a photoanode current based on oxygen generation, and the available visible light is limited to 540 nm or less.
そこで、本発明は、低いバイアスで光アノード電流を与え、長波長域の可視光を利用することのできる、新規の水の可視光分解用アノード電極を提供することを目的とする。 Accordingly, an object of the present invention is to provide a novel anode electrode for visible light decomposition of water which can provide a photoanode current with a low bias and can use visible light in a long wavelength region.
本発明の水の可視光分解用アノード電極は、酸化チタン電極に硫化アンチモンを析出させて得られたことを特徴とする。 The anode electrode for visible light decomposition of water according to the present invention is obtained by depositing antimony sulfide on a titanium oxide electrode.
また、前記酸化チタン電極は、ナノポーラス酸化チタン電極であることを特徴とする。 The titanium oxide electrode is a nanoporous titanium oxide electrode.
本発明の水の可視光分解装置は、本発明の水の可視光分解用アノード電極を備えたことを特徴とする。 The visible light decomposition apparatus for water according to the present invention includes the anode electrode for visible light decomposition according to the present invention.
本発明の水の可視光分解用アノード電極及び水の可視光分解装置によれば、−０．５Ｖ ｖｓ Ａｇ／ＡｇＣｌのバイアスで光アノード電流を与え、６５０ｎｍ以下の可視光を利用できる。 According to the anode electrode for visible light decomposition of water and the visible light decomposition apparatus for water according to the present invention, a photoanode current is applied with a bias of −0.5 V vs Ag / AgCl, and visible light of 650 nm or less can be used.
本発明の水の可視光分解用アノード電極は、酸化チタン電極に硫化アンチモンを析出させて得られたものである。また、本発明の水の可視光分解装置は、上記の水の可視光分解用アノード電極を備えたものである。なお、以下の説明において、本発明の水の可視光分解用アノード電極を硫化アンチモン／酸化チタン複合電極という。 The anode electrode for visible light decomposition of the present invention is obtained by depositing antimony sulfide on a titanium oxide electrode. Moreover, the visible-light-decomposing apparatus of water of this invention is equipped with said anode electrode for visible-light decomposition of water. In the following description, the anode electrode for visible light decomposition of water according to the present invention is referred to as an antimony sulfide / titanium oxide composite electrode.
ここで、酸化チタン電極としては、例えば、ＩＴＯ基板上に酸化チタン層を形成して作成した電極を用いることができる。また、酸化チタン電極としては、比表面積が大きいことから、微細な多孔質構造を有するナノポーラス酸化チタン電極が好適に用いられる。なお、ナノポーラス酸化チタン電極は、粒径が３０〜４０ｎｍで、酸化チタン層の厚さが７〜１０μｍのものが最も好適に用いられる。 Here, as the titanium oxide electrode, for example, an electrode formed by forming a titanium oxide layer on an ITO substrate can be used. Moreover, as a titanium oxide electrode, since the specific surface area is large, the nanoporous titanium oxide electrode which has a fine porous structure is used suitably. A nanoporous titanium oxide electrode having a particle size of 30 to 40 nm and a titanium oxide layer thickness of 7 to 10 μm is most preferably used.
また、酸化チタン電極に硫化アンチモンを析出させる際に、酸化チタン電極を浸漬する硫化アンチモン溶液は、１〜１．３Ｍ ＳｂＣｌ３アセトン溶液と０．８〜１．２Ｍ Ｎａ２Ｓ２Ｏ３水溶液を１：８〜１２の容積比で混合した後、水を加えて容積比で３〜４倍に薄めたものが好適に用いられる。 In addition, when depositing antimony sulfide on the titanium oxide electrode, the antimony sulfide solution in which the titanium oxide electrode is immersed is a 1 to 1.3 M SbCl 3 acetone solution and a 0.8 to 1.2 M Na 2 S 2 O 3 aqueous solution. After mixing at a volume ratio of 1: 8 to 12, water added to dilute 3 to 4 times by volume ratio is preferably used.
また、酸化チタン電極に硫化アンチモンを析出させる条件としては、０〜１０℃で１２〜３６ｈが好ましい。 Moreover, as conditions for depositing antimony sulfide on the titanium oxide electrode, 12 to 36 h is preferable at 0 to 10 ° C.
本発明による硫化アンチモン／酸化チタン複合電極を作用極として用い、白金線を対極として用いた電解槽を構成し、硫化アンチモン／酸化チタン複合電極に可視光照射することにより、水を酸素と水素に分解することができる。 An electrolytic cell using an antimony sulfide / titanium oxide composite electrode according to the present invention as a working electrode and a platinum wire as a counter electrode is constructed, and the antimony sulfide / titanium oxide composite electrode is irradiated with visible light, whereby water is converted into oxygen and hydrogen. Can be disassembled.
なお、硫化アンチモン／酸化チタン複合電極は色素増感太陽電池の負極として報告されている（Nano Lett. 2010, 10, 2609-2612）。しかし、硫化アンチモン／酸化チタン複合電極を水の可視光分解系の光アノードとして用いた例はない。 An antimony sulfide / titanium oxide composite electrode has been reported as a negative electrode of a dye-sensitized solar cell (Nano Lett. 2010, 10, 2609-2612). However, there is no example in which the antimony sulfide / titanium oxide composite electrode is used as a photoanode for water visible light decomposition system.
以下、より具体的に、本発明の水の可視光分解用アノード電極について説明する。なお、本発明は以下の実施形態に限定されるものではなく、本発明の思想を逸脱しない範囲で種々の変形実施が可能である。 Hereinafter, the anode electrode for visible light decomposition of water according to the present invention will be described more specifically. Note that the present invention is not limited to the following embodiments, and various modifications can be made without departing from the spirit of the present invention.
以下に示すように、硫化アンチモン／酸化チタン複合電極を作製した。１．１５Ｍ ＳｂＣｌ３アセトン溶液（３．０ｍｌ）と１Ｍ Ｎａ２Ｓ２Ｏ３水溶液（３０ｍｌ）を混合し、水を加えて１００ｍｌとした。この混合溶液にナノポーラス酸化チタン電極を４℃で２４ｈ浸漬して、酸化チタン電極上に硫化アンチモンを析出させた。作製した電極を水でよく洗い、空気中で乾燥した。 As shown below, an antimony sulfide / titanium oxide composite electrode was prepared. 1.15M SbCl 3 acetone solution (3.0 ml) and 1M Na 2 S 2 O 3 aqueous solution (30 ml) were mixed, and water was added to make 100 ml. A nanoporous titanium oxide electrode was immersed in this mixed solution at 4 ° C. for 24 hours to deposit antimony sulfide on the titanium oxide electrode. The produced electrode was washed thoroughly with water and dried in air.
硫化アンチモン／酸化チタン複合電極のサイクリックボルタモグラムを図１に示す。 A cyclic voltammogram of the antimony sulfide / titanium oxide composite electrode is shown in FIG.
光源は１５０Ｗハロゲンランプに４２０ｎｍ以下の光をカットするフィルターを装着したものを用い、光強度は１００ｍＷ・ｃｍ−２に設定し、ｐＨ＝７の０．１Ｍのリン酸バッファー溶液中で試験を行った。５ｍＶ・ｓ−１で電位を掃引しながら測定した。 The light source is a 150 W halogen lamp equipped with a filter that cuts light of 420 nm or less, the light intensity is set to 100 mW · cm −2 , and the test is performed in a 0.1 M phosphate buffer solution at pH = 7. It was. The measurement was performed while sweeping the potential at 5 mV · s −1 .
その結果、暗時では、−０．３Ｖ ｖｓ Ａｇ／ＡｇＣｌ以上でアノード電流は見られなかったが（点線ＣＶ）、４２０ｎｍ以上の可視光を照射したとき、−０．５Ｖ ｖｓ Ａｇ／ＡｇＣｌ付近で水の酸化に基づくアノード電流が立ち上がり、２００μＡ・ｃｍ−２の光電流が観察された。また、１時間の光電解を行った後、電解セル気相中で発生した水素と酸素を検出した。このように、硫化アンチモン／酸化チタン複合電極を光アノードとして用いて水の可視光分解が達成された。 As a result, in the dark, anode current was not seen at −0.3 V vs Ag / AgCl or higher (dotted line CV), but when irradiated with visible light of 420 nm or higher, around −0.5 V vs Ag / AgCl. The anode current based on the oxidation of water rose and a photocurrent of 200 μA · cm −2 was observed. Further, after photoelectrolysis for 1 hour, hydrogen and oxygen generated in the gas phase of the electrolytic cell were detected. Thus, visible light decomposition of water was achieved using the antimony sulfide / titanium oxide composite electrode as a photoanode.
図２に硫化アンチモン／酸化チタン複合電極（Ｓｂ２Ｓ３／ＴｉＯ２）を光アノードとしたときの入射光電流変換効率（ＩＰＣＥ）の作用スペクトルを示す。 FIG. 2 shows an action spectrum of incident photocurrent conversion efficiency (IPCE) when an antimony sulfide / titanium oxide composite electrode (Sb 2 S 3 / TiO 2 ) is used as a photoanode.
このとき、５００Ｗキセノンランプを光源とし、モノクロメーターで取り出した各波長の単色光を硫化アンチモン／酸化チタン複合電極に照射した。また、印加電圧は−０．２Ｖ ｖｓ Ａｇ／ＡｇＣｌとし、ｐＨ＝７の０．１Ｍ リン酸バッファー溶液中で試験を行った。また、比較のために、硫化アンチモンを複合させていない酸化チタン電極（ＴｉＯ２）を用いて同様に試験を行った。 At this time, using a 500 W xenon lamp as a light source, monochromatic light of each wavelength extracted by a monochromator was irradiated to the antimony sulfide / titanium oxide composite electrode. The applied voltage was −0.2 V vs. Ag / AgCl, and the test was performed in a 0.1 M phosphate buffer solution with pH = 7. For comparison, a similar test was performed using a titanium oxide electrode (TiO 2 ) not combined with antimony sulfide.
硫化アンチモンを複合させていない酸化チタン電極（○）では４００ｎｍ以上の可視光で光電流はほとんど見られなかったが、硫化アンチモン／酸化チタン複合電極（●）を光アノードとしたときでは、はっきりと光電流の発生が観察された。このように、硫化アンチモン／酸化チタン複合電極によれば、６５０ｎｍ以下の可視光で光電流が得られることが確認された。 No photocurrent was seen with visible light of 400 nm or more with a titanium oxide electrode (○) that was not combined with antimony sulfide. Generation of photocurrent was observed. Thus, according to the antimony sulfide / titanium oxide composite electrode, it was confirmed that a photocurrent was obtained with visible light of 650 nm or less.
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