JP6115952B2 - Visible light responsive composition and photoelectrode, photocatalyst, and photosensor using the same - Google Patents
Visible light responsive composition and photoelectrode, photocatalyst, and photosensor using the same Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims description 20
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- 229910052742 iron Inorganic materials 0.000 claims description 12
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Description
本発明は可視光応答性の組成物とこれを用いた光電極・光触媒・光センサーに関するものである。 The present invention relates to a visible light responsive composition and a photoelectrode / photocatalyst / photosensor using the composition.
近年、太陽光エネルギーを利用するための光電極、太陽光により環境汚染物質を分解除去する光触媒、両者を用いる水の分解反応による水素製造、及び光を定量的に測定するための光電変換素子型の光センサーが注目されており、それらの材料として様々な半導体の研究開発が行われている。酸化チタンはその代表的なものであり、実用的に最も多く用いられている。
しかし、この酸化チタンはバンドギャップが大きいため太陽光の大部分を占める可視光領域に吸収性がなく、太陽光を有効に利用することができない。また酸化チタンは吸収性のある紫外光領域が極めて弱い室内光や自動車の車内光では機能しない。
このための対策として、新たに利用可能な可視光応答性組成物を開発するため、酸化チタン等の既存の組成物に他の元素を微量ドープするなどの改良研究や全く新規な可視光応答性組成物を探索する研究が行われている（例えば、非特許文献１、２）。
しかしながら、様々な元素を異なった割合で含む組成物の組み合わせの数は膨大なため、新規な組成物を合成しその可視光応答性を評価するには多くの時間と労力が必要であり、その研究開発はこれまであまり進展していなかった。
そこで本発明者らは、多種類の元素を様々な比率で含む組成物の薄膜自動合成装置と、その薄膜の光照射に対する光電流応答性の自動評価装置を新たに開発し、可視光応答性を有し、光電極や光触媒、及び光センサー材料として有望な新規な組成物の高速探索研究を進めてきている（特許文献１）。本発明者らは、その過程でＦｅ−Ｚｒ系やＦｅ−Ｔｉ系の組成について着目し、研究開発を進め、Ｆｅが２０％から８０％、Ｚｒが２０％から５０％、Ｔｉが０％から３０％の範囲にある可視光応答性複合酸化物（特許文献２）、Ｆｅが５０％から８５％、Ｚｒが８％から４８％、Ｍ（Ａｌ、Ｚｎ、Ｉｎ、Ｓｎ、Ｔａ）が０.０１％から２９％の範囲にある可視光応答性複合酸化物（特許文献３）、Ｆｅが８７％から９０％、Ｔｉが９％から１０％、Ｍ（Ｓｉ、Ｂａ、Ｙ）が０.１％から３％の範囲にある可視光応答性複合酸化物（特許文献４）、Ｆｅが８５％から９７％、Ｔｉが１％から１０％、Ｍ（Ｌａ、Ｓｒ）が０.１％から７％の範囲にある可視光応答性複合酸化物（特許文献５）、Ｆｅが８１％から９０％、Ｔｉが９％から１０％、Ｍ（Ｃａ、Ｂｉ）が０.１％から１０％の範囲にある可視光応答性複合酸化物（特許文献６）、Ｆｅが８９％から９２％、Ｔｉが１％から１０％、Ｚｎが０.１％から１０％の範囲にある可視光応答性複合酸化物（特許文献７）を見いだした。
しかしながら、Ｆｅ−Ｚｒ系やＦｅ−Ｔｉ系以外の組成のものについては、未だ研究開発はあまり進展していない。
In recent years, a photoelectrode for using solar energy, a photocatalyst that decomposes and removes environmental pollutants by sunlight, hydrogen production by water decomposition reaction using both, and a photoelectric conversion element type for quantitatively measuring light Optical sensors are attracting attention, and various semiconductors are being researched and developed as their materials. Titanium oxide is a typical example and is most frequently used in practice.
However, since this titanium oxide has a large band gap, the visible light region that occupies most of the sunlight has no absorbability, and sunlight cannot be used effectively. Titanium oxide does not function in indoor light or in-car light of an automobile where the absorbing ultraviolet light region is extremely weak.
As a countermeasure for this, in order to develop a newly usable visible light responsive composition, improvement research such as doping a small amount of other elements into an existing composition such as titanium oxide or a completely new visible light responsiveness Studies for searching for compositions have been conducted (for example, Non-Patent Documents 1 and 2).
However, since the number of combinations of compositions containing various elements in different proportions is enormous, it takes a lot of time and labor to synthesize a new composition and evaluate its visible light response. R & D has not made much progress so far.
Therefore, the present inventors newly developed a thin film automatic synthesis apparatus for compositions containing various kinds of elements in various ratios, and an automatic evaluation apparatus for photocurrent response to light irradiation of the thin film, and visible light responsiveness. Research has been conducted on a high-speed search for a novel composition that is promising as a photoelectrode, photocatalyst, and photosensor material (Patent Document 1). In the process, the present inventors paid attention to the composition of Fe—Zr and Fe—Ti, and proceeded with research and development. Fe was 20% to 80%, Zr was 20% to 50% and Ti was 0%. Visible light-responsive composite oxide in the range of 30% (Patent Document 2), Fe is 50% to 85%, Zr is 8% to 48%, and M (Al, Zn, In, Sn, Ta) is 0.00. Visible light responsive complex oxide in the range of 01% to 29% (Patent Document 3), Fe 87% to 90%, Ti 9% to 10%, M (Si, Ba, Y) 0.1 % To 3% of visible light responsive complex oxide (Patent Document 4), Fe from 85% to 97%, Ti from 1% to 10%, M (La, Sr) from 0.1% to 7 % Visible light responsive complex oxide (Patent Document 5), Fe 81% to 90%, Ti 9% to 10%, M Visible light-responsive composite oxide (Ca, Bi) in the range of 0.1% to 10% (Patent Document 6), Fe 89% to 92%, Ti 1% to 10%, Zn 0.1% A visible light responsive complex oxide (Patent Document 7) in the range of 10% to 10% was found.
However, research and development have not progressed so far for compositions other than Fe-Zr and Fe-Ti.
以上のような背景から、本発明は、発明者らによるこれまでの検討をさらに発展させて、従来全く検討されてこなかった系の組成物についても幅広く検討を進め、可視光照射に対して光電流応答性を有し、光電極材料・光触媒材料・光センサー材料となり得る新規な組成物と、これにより構成される新しい光電極・光触媒・光センサー、及びこれら光電極・光触媒による新しい水分解方法を提供することを課題としている。 From the background as described above, the present invention further develops the studies by the inventors so far, and extensively studies the composition of the system that has not been studied at all so far. Novel composition having current responsiveness and capable of becoming photoelectrode material / photocatalyst material / photosensor material, new photoelectrode / photocatalyst / photosensor composed thereof, and new water decomposition method using these photoelectrode / photocatalyst It is an issue to provide.
本発明者らは、上記課題を解決するために鋭意検討し、上記した特許文献１に記載の装置を用いて新規な可視光応答性組成物を探索研究した結果、可視光照射に対しても光電流応答性を示す、光電極・光触媒・光センサーの材料となる新規な組成物を知見し、本発明を完成するに至った。酸素以外の３種類以上元素の特定の比率において非常に効果が大きいことを見いだしたものであり、手動での探索ではほぼ見つからなかった特殊な組成物である。 The present inventors diligently studied to solve the above-mentioned problems, and as a result of exploring and researching a novel visible light responsive composition using the apparatus described in Patent Document 1 described above, the present inventors have also performed visible light irradiation. The inventors have found a novel composition that exhibits photocurrent response and can be used as materials for photoelectrodes, photocatalysts, and photosensors, and have completed the present invention. It has been found to be very effective at a specific ratio of three or more elements other than oxygen, and is a special composition that was hardly found by manual search.
すなわち、この本発明は以下のことを特徴としている。
（１）Ｓｎ、Ｆｅ、Ｖ、酸素からなる組成物であって、Ｓｎ、Ｆｅ、Ｖの合計を１００％としたときの元素含有比（モル比）がＳｎ：３０〜５０％、Ｆｅ：３０〜４０％、Ｖ：２０〜３０％の範囲内にあることを特徴とする可視光応答性組成物。
（２）上記の可視光応答性組成物をもって構成されている光電極。
（３）上記の可視光応答性組成物をもって構成されている光触媒。
（４）上記の可視光応答性組成物をもって構成されている光センサー。
（５）上記（２）に記載の光電極及び／又は上記（３）に記載の光触媒による水分解方法。
That is, the present invention is characterized by the following.
(1) A composition composed of Sn, Fe, V, and oxygen, and the element content ratio (molar ratio) when Sn, Fe, and V are 100% is Sn: 30 to 50%, Fe: 30 Visible light-responsive composition characterized by being in the range of ˜40%, V: 20-30%.
(2) The photoelectrode comprised with said visible-light-responsive composition.
(3) The photocatalyst comprised with said visible light responsive composition.
(4) The optical sensor comprised with said visible light responsive composition.
(5) The water splitting method using the photoelectrode according to (2) and / or the photocatalyst according to (3).
本発明は、次のような態様とすることもできる。
（６）Ｖに対するＦｅのモル比が１.２〜１.７である上記（１）に記載された可視光応答性組成物。
（７）粒状体、薄膜、焼結体、又は、積層体である上記（１）又は（６）に記載された可視光応答性組成物。
（８）基板上又は基材上に形成されたものである上記（１）、（６）、又は、（７）に記載された可視光応答性組成物。
（９）熱分解法、焼結法、又は、気相成膜法により形成されたものである上記（１）、（６）〜（８）のいずれか１項に記載された可視光応答性組成物。
（１０）上記（６）〜（９）のいずれか１項に記載された可視光応答性組成物をもって構成されている光電極。
（１１）上記（６）〜（９）のいずれか１項に記載された可視光応答性組成物をもって構成されている光触媒。
（１２）上記（６）〜（９）のいずれか１項に記載された可視光応答性組成物をもって構成されている光センサー。
（１３）上記（１０）に記載の光電極及び／又は上記（１１）に記載の光触媒による水分解方法。
The present invention may be configured as follows.
(6) The visible light responsive composition as described in (1) above, wherein the molar ratio of Fe to V is 1.2 to 1.7.
(7) The visible light responsive composition described in the above (1) or (6), which is a granular body, a thin film, a sintered body, or a laminate.
(8) The visible light responsive composition described in the above (1), (6), or (7), which is formed on a substrate or a base material.
(9) Visible light responsiveness described in any one of (1) and (6) to (8) above, which is formed by a thermal decomposition method, a sintering method, or a vapor phase film forming method. Composition.
(10) A photoelectrode comprising the visible light responsive composition described in any one of (6) to (9) above.
(11) A photocatalyst comprising the visible light responsive composition described in any one of (6) to (9) above.
(12) An optical sensor comprising the visible light responsive composition described in any one of (6) to (9) above.
(13) The water splitting method using the photoelectrode according to (10) and / or the photocatalyst according to (11).
光電流は光電極材料として用いたときの性能を示すものであり、また光触媒が機能するための電荷分離の度合を示している。本発明の組成物は可視光照射によって電荷分離を生じて光電流を発生させることから、可視光応答性光電極や可視光応答性光触媒の材料として用いることができる。これらを用いて水を還元し水素を発生させ、光エネルギーを水素に変換することができる。また、特定の波長域のみの光センサーとして、可視光域にのみ分光感度を有する光センサーの材料を提供することができる。 The photocurrent indicates the performance when used as a photoelectrode material, and indicates the degree of charge separation for the photocatalyst to function. Since the composition of the present invention generates a photocurrent by generating charge separation by irradiation with visible light, it can be used as a material for a visible light responsive photoelectrode or a visible light responsive photocatalyst. These can be used to reduce water to generate hydrogen and convert light energy to hydrogen. In addition, as an optical sensor having only a specific wavelength range, a photosensor material having spectral sensitivity only in the visible light range can be provided.
本発明の可視光応答性組成物は、Ｓｎ、Ｆｅ、Ｖ、酸素の４元素を必須のものとして含むものである。ここで、Ｓｎ、Ｆｅ、Ｖの合計を１００％としたときの元素含有比（モル比）がＳｎ：３０〜５０％、Ｆｅ：３０〜４０％、Ｖ：２０〜３０％の範囲内にある。Ｖに対するＦｅのモル比は、好ましくは１.２〜１.７（より好ましくは１.３〜１.６）である。本発明の可視光応答性組成物は、基本的には、上記４元素からなるが、可視光応答性を大幅に低下させない限度において、他の元素の含有を排除しようとするものではない。また、他の元素を含有している場合でも、他の元素は、含有比からは除外し、合計に加算しない。 The visible light responsive composition of the present invention contains four elements of Sn, Fe, V, and oxygen as essential elements. Here, the element content ratio (molar ratio) when the total of Sn, Fe, and V is 100% is in the range of Sn: 30 to 50%, Fe: 30 to 40%, and V: 20 to 30%. . The molar ratio of Fe to V is preferably 1.2 to 1.7 (more preferably 1.3 to 1.6). The visible light responsive composition of the present invention basically comprises the above four elements, but does not intend to exclude the inclusion of other elements as long as the visible light responsiveness is not significantly reduced. Even when other elements are contained, other elements are excluded from the content ratio and are not added to the total.
本発明の組成物を用いて光電極を構成すると、上記した元素の含有比（モル比）の範囲において、可視光照射によって電荷分離を生じて大きな光電流が発生する。 When a photoelectrode is constituted using the composition of the present invention, charge separation occurs due to visible light irradiation and a large photocurrent is generated within the range of the above-described element content ratio (molar ratio).
本発明の組成物は、熱分解法や混合粉末の焼結法、電着法あるいはスパッタリング等のような気相成膜法等の各種の方法により製造可能とされるが、なかでも、熱分解法で作製することが好ましい。例えば、薄膜形状に作製する場合（塗布熱分解法）については詳細を実施例において説明する。この熱分解法ではそれぞれの元素を含む溶液（場合によってはコロイド溶液や懸濁液など）を良く混合して原料液を調製し、それを焼成することで組成物を作製する。熱分解法には、元素含有比（モル比）の正確な制御ができる、溶液で混合するので均一な組成物を作製できる、薄膜形状にする場合（塗布熱分解法）は塗布と焼成を繰り返して積層することで精密なものが作製できる等の利点がある。本発明に用いる熱分解法は、それぞれの元素を含む液を混合して焼成する方法ならばよく、ゾルゲル法、錯体重合法、有機金属分解法等も挙げることができる。薄膜の多孔性や溶液粘度を制御するためにポリエチレングリコールやエチルセルロースなどポリマーや有機物を溶液に添加しても良い。 The composition of the present invention can be produced by various methods such as a thermal decomposition method, a mixed powder sintering method, an electrodeposition method, a vapor deposition method such as sputtering, and the like. It is preferable to prepare by the method. For example, in the case of producing a thin film (coating pyrolysis method), details will be described in Examples. In this pyrolysis method, a solution containing each element (in some cases, a colloidal solution, a suspension, etc.) is mixed well to prepare a raw material solution, which is fired to produce a composition. In the thermal decomposition method, the element content ratio (molar ratio) can be accurately controlled, and a uniform composition can be prepared by mixing with a solution. In the case of a thin film shape (coating pyrolysis method), coating and baking are repeated. There is an advantage that a precise one can be produced by laminating the layers. The thermal decomposition method used in the present invention may be any method in which a liquid containing each element is mixed and fired, and examples thereof include a sol-gel method, a complex polymerization method, and an organometallic decomposition method. In order to control the porosity and solution viscosity of the thin film, a polymer or an organic substance such as polyethylene glycol or ethyl cellulose may be added to the solution.
本発明の組成物は、均一組成の複合酸化物でも良いし、ドーピング化合物でも良い。また複数の化合物が混合した状態で存在していても良い。
酸素や空気中で焼成して本組成物を合成すれば、通常は最も安定な組成の酸化物になるが、雰囲気ガスを制御して酸化物以外の組成物を合成しても良い。例えば、ＮＨ3やＨ2Ｓ、ＣＨ4ガスを流しながら合成すれば、Ｎ、Ｓ、Ｃを一部含んだ組成物を合成できる。
光電極や光センサーとして利用する場合は、本発明の組成物を導電性基板上に固定する。例えば、導電性ガラスや金属などの耐熱性の導電性基板上に各元素を含んだ溶液を塗布して熱分解法で成膜する。
The composition of the present invention may be a complex oxide having a uniform composition or a doping compound. A plurality of compounds may exist in a mixed state.
If the composition is synthesized by firing in oxygen or air, the oxide having the most stable composition is usually obtained, but a composition other than the oxide may be synthesized by controlling the atmospheric gas. For example, if synthesis is performed while flowing NH 3 , H 2 S, or CH 4 gas, a composition partially containing N, S, and C can be synthesized.
When used as a photoelectrode or photosensor, the composition of the present invention is fixed on a conductive substrate. For example, a solution containing each element is applied onto a heat-resistant conductive substrate such as conductive glass or metal, and a film is formed by a thermal decomposition method.
本組成物は、光電極として用いる場合は、基板に強く接合し且つ多孔質であることが望ましい。また、光触媒として用いる場合は比較的高い表面積で且つ結晶性が高いことが望ましい。 When the composition is used as a photoelectrode, it is desirable that the composition is strongly bonded to the substrate and is porous. When used as a photocatalyst, it is desirable that the surface area is relatively high and the crystallinity is high.
そして、本発明によれば、上記の組成物を用いての光電極、光触媒及び光センサーが提供されることになる。 And according to this invention, the photoelectrode, photocatalyst, and photosensor using said composition are provided.
以下、本発明を実施例によりさらに具体的に説明するが、本発明はこの実施例によって何ら限定されるものではない。 Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the examples.
（実施例１〜４、比較例１〜１０）
組成物薄膜の自動合成装置（特許文献１）を用いて塗布熱分解法によりＳｎ−Ｆｅ−Ｖの３元系薄膜ライブラリーを合成した。この薄膜ライブラリーはそれぞれの元素の含有比が異なった組成物の薄膜を一枚の導電性ガラス基板上に間隔を置いて作製したものである。元素の含有量は表１のように変化させた。
(Examples 1-4, Comparative Examples 1-10)
An Sn-Fe-V ternary thin film library was synthesized by a coating pyrolysis method using an automatic composition thin film synthesis apparatus (Patent Document 1). This thin film library is prepared by forming thin films of compositions having different content ratios of elements on a single conductive glass substrate at intervals. The element content was changed as shown in Table 1.
塗布する原料溶液は、シンメトリックス社製のＳｎ、Ｆｅ、Ｖの有機錯体溶液をモル濃度が０.２Ｍとなるように酢酸ブチルで希釈し、それらの体積比を変えて混合することによりそれぞれの含有量のモル比を調整した。それらの溶液には増粘剤として１０重量％のエチルセルロースの酢酸ブチル溶液を体積比で等量加えて混合した。
導電性ガラス基板にそれぞれの溶液を所定の位置に塗布し焼成することを４回繰り返して積層膜を合成した。焼成は空気中５５０℃で０.５時間、７００℃でさらに０.５時間行った。これらを（実施例１〜４、比較例１〜１０）とした。
The raw material solution to be applied is diluted with butyl acetate so that the molar concentration of Sn, Fe, V organic complex solution manufactured by Symmetrics is 0.2M, and the volume ratio thereof is changed and mixed. The molar ratio of content was adjusted. To these solutions, 10% by weight of ethyl cellulose in butyl acetate as a thickener was added in an equal volume ratio and mixed.
Each solution was applied to a predetermined position on a conductive glass substrate and fired four times to synthesize a laminated film. Firing was performed in air at 550 ° C. for 0.5 hours and at 700 ° C. for another 0.5 hours. These were made into (Examples 1-4, Comparative Examples 1-10).
組成物の可視光応答性は光電流を測定して評価した。光電流は組成物の電荷分離能力や可視光反応性を示す尺度であり、大きいほど性能が高い。作製した組成物の薄膜ライブラリーを、水酸化ナトリウムでｐＨ７.０に調整した０.１Ｍのリン酸二水素ナトリウム溶液中に入れ、４２０ｎｍより短波長をカットするフィルターを装着した３００ＷのＸｅランプを直径１ｍｍのホールスリットを通して３.２ｍＷで照射しながら、１Ｖ（ｖｓ.Ａｇ／ＡｇＣｌ）において光電流を測定した。対極には白金を用いており、その上では電流値に対応した水素が発生する。表１に光電流の測定結果を示した。
なお、酸化チタンについても、本発明の実施例と同様に薄膜ライブラリーを合成して光電流を測定したが、光電流はほとんど生じなかった（０μＡ）。
Visible light responsiveness of the composition was evaluated by measuring photocurrent. The photocurrent is a scale indicating the charge separation ability and visible light reactivity of the composition, and the larger the performance, the higher the performance. A 300 W Xe lamp equipped with a filter that cuts wavelengths shorter than 420 nm is placed in a 0.1 M sodium dihydrogen phosphate solution adjusted to pH 7.0 with sodium hydroxide. The photocurrent was measured at 1 V (vs. Ag / AgCl) while irradiating at 3.2 mW through a 1 mm diameter hole slit. Platinum is used for the counter electrode, on which hydrogen corresponding to the current value is generated. Table 1 shows the measurement results of the photocurrent.
As for titanium oxide, photocurrent was measured by synthesizing a thin film library in the same manner as in the examples of the present invention, but almost no photocurrent was generated (0 μA).
表１から明らかなように、Ｓｎ、Ｆｅと、第３の成分としてＶとを選択し、その組成をＳｎ：３０〜５０％、Ｆｅ：３０〜４０％、Ｖ：２０〜３０％とした場合は、比較例に比べ顕著に大きな光電流の値を示し、その全ての例において、酸化チタンをはるかに上回る可視光応答性を示した。 As is apparent from Table 1, when Sn, Fe and V are selected as the third component, the composition is Sn: 30-50%, Fe: 30-40%, V: 20-30% Showed significantly larger photocurrent values than the comparative examples, and in all of the examples, visible light responsiveness far exceeding that of titanium oxide was exhibited.
本発明の組成物により光電極を構成すると可視光の吸収利用が促進され、水の分解による水素製造のような光電極による太陽光のより効率的な利用が可能になる。また建物の室内や自動車内のように紫外光が弱い場所においても、本発明の組成物により構成する光触媒によって室内光や車内光を用いて環境汚染物質の除去や消臭、抗菌、抗ウィルス、抗カビ、防汚、防曇等を可能にする。さらに可視光域の光にのみ反応する光センサーの材料を提供することが出来る。 When the photoelectrode is constituted by the composition of the present invention, the absorption and utilization of visible light is promoted, and more efficient use of sunlight by the photoelectrode such as hydrogen production by water decomposition becomes possible. In addition, even in places where ultraviolet light is weak such as indoors of buildings and automobiles, removal of environmental pollutants and deodorization, antibacterial, antiviral, using indoor light and in-car light by the photocatalyst constituted by the composition of the present invention, Enables antifungal, antifouling, antifogging, etc. Furthermore, a material for an optical sensor that reacts only to light in the visible light range can be provided.
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