JP2016159289A - Light absorption material - Google Patents
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- JP2016159289A JP2016159289A JP2015043737A JP2015043737A JP2016159289A JP 2016159289 A JP2016159289 A JP 2016159289A JP 2015043737 A JP2015043737 A JP 2015043737A JP 2015043737 A JP2015043737 A JP 2015043737A JP 2016159289 A JP2016159289 A JP 2016159289A
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Abstract
Description
本発明は、光吸収材料に関し、さらに詳しくは光エネルギーを有効に利用し得る光吸収波長域の広い光吸収材料に関する。 The present invention relates to a light-absorbing material, and more particularly to a light-absorbing material having a wide light-absorbing wavelength range that can effectively use light energy.
近年、温室効果ガスとして知られるＣＯ２から反応性化合物、例えば一酸化炭素（ＣＯ）を得る還元反応が温室効果ガスの固定法の１つとして検討されている。
前記の還元反応として、光吸収材料とＣＯ２還元触媒とを併用して光照射によりＣＯ２の還元を行う方法が提案されている。
In recent years, a reduction reaction for obtaining a reactive compound such as carbon monoxide (CO) from CO 2 known as a greenhouse gas has been studied as one method for fixing a greenhouse gas.
As the reduction reaction, a method has been proposed in which a light absorbing material and a CO 2 reduction catalyst are used in combination to reduce CO 2 by light irradiation.
このため、光吸収材料およびＣＯ２還元触媒について様々な検討がされている。
例えば、特許文献１には、光増感酸化還元反応における照射光を吸収するための光増感剤としてルテニウムトリス（２，２’−ビピリジル）錯体が記載されている。
しかし、前記の公知文献に記載の化合物を光吸収材料として用いてＣＯ２還元触媒と併用し光照射してもルテニウムトリス（２，２’−ビピリジル）（II）錯体の光吸収波長域が狭いために、光エネルギーを利用したＣＯ２還元反応において光エネルギーを有効に利用できずＣＯ２の還元性能が低い。
For this reason, various studies have been made on the light-absorbing material and the CO 2 reduction catalyst.
For example, Patent Document 1 describes a ruthenium tris (2,2′-bipyridyl) complex as a photosensitizer for absorbing irradiation light in a photosensitized redox reaction.
However, the light absorption wavelength region of the ruthenium tris (2,2′-bipyridyl) (II) complex is narrow even when the compound described in the above-mentioned known literature is used as a light absorption material and used in combination with a CO 2 reduction catalyst and irradiated with light. Therefore, in the CO 2 reduction reaction using light energy, the light energy cannot be effectively used, and the CO 2 reduction performance is low.
従って、本発明の目的は、光エネルギーを有効に利用し得る光吸収波長域の広い光吸収材料を提供することである。 Accordingly, an object of the present invention is to provide a light-absorbing material having a wide light absorption wavelength range in which light energy can be effectively used.
本発明は、トリス（２，２’−ビピリジル）ルテニウム（II）錯体（以下、［Ｒｕ（ｂｐｙ）３］２＋と略記する場合もある。）およびビス（２，２’−ビピリジル）（２，２’−ビピリジル−４，４’−ジカルボン酸）ルテニウム（II）錯体（以下、［Ｒｕ（ｂｐｙ）２（ｄｃｂｐｙ）］２＋と略記する場合もある。）を組み合わせてなる光吸収材料に関する。 The present invention relates to a tris (2,2′-bipyridyl) ruthenium (II) complex (hereinafter sometimes abbreviated as [Ru (bpy) 3 ] 2+ ) and bis (2,2′-bipyridyl) (2, The present invention relates to a light-absorbing material obtained by combining a 2′-bipyridyl-4,4′-dicarboxylic acid) ruthenium (II) complex (hereinafter sometimes abbreviated as [Ru (bpy) 2 (dcbpy)] 2+ ).
本発明によれば、光エネルギーを有効に利用し得る光吸収波長域の広い光吸収材料を得ることができる。 According to the present invention, it is possible to obtain a light-absorbing material having a wide light absorption wavelength range in which light energy can be effectively used.
特に、本発明において、以下の実施態様を挙げることができる。
1) 二酸化炭素還元触媒と組み合わせて用いられる前記の光吸収材料。
2) 前記トリス（２，２’−ビピリジル）ルテニウム（II）錯体と前記ビス（２，２’−ビピリジル）（２，２’−ビピリジル−４，４’−ジカルボン酸）ルテニウム（II）錯体との割合がモル比で１：２〜２：１である前記の光吸収材料。
In particular, in the present invention, the following embodiments can be mentioned.
1) The above light-absorbing material used in combination with a carbon dioxide reduction catalyst.
2) The tris (2,2′-bipyridyl) ruthenium (II) complex and the bis (2,2′-bipyridyl) (2,2′-bipyridyl-4,4′-dicarboxylic acid) ruthenium (II) complex The above light-absorbing material, wherein the molar ratio is 1: 2 to 2: 1.
本発明においては、トリス（２，２’−ビピリジル）ルテニウム（II）錯体とビス（２，２’−ビピリジル）（２，２’−ビピリジル−４，４’−ジカルボン酸）ルテニウム（II）錯体とを組み合わせた光吸収材料であることが必要である。
前記の２成分を組み合わせることによって、図１に示すように、照射光の吸収波長域の広域化が実現されている。このことは全く予想外のことである。これに対して、前記の２成分を単独で用いた光吸収材料は吸収波長域が狭い。
In the present invention, tris (2,2′-bipyridyl) ruthenium (II) complex and bis (2,2′-bipyridyl) (2,2′-bipyridyl-4,4′-dicarboxylic acid) ruthenium (II) complex It is necessary to be a light absorbing material in combination.
By combining the two components described above, the broadening of the absorption wavelength range of the irradiation light is realized as shown in FIG. This is completely unexpected. On the other hand, the light absorption material using the two components alone has a narrow absorption wavelength region.
前記のトリス（２，２’−ビピリジル）ルテニウム（II）錯体とビス（２，２’−ビピリジル）（２，２’−ビピリジル−４，４’−ジカルボン酸）ルテニウム（II）錯体との割合としては、好適にはモル比で１：２〜２：１、典型的にはモル比で１：１である。 Ratio of tris (2,2′-bipyridyl) ruthenium (II) complex to bis (2,2′-bipyridyl) (2,2′-bipyridyl-4,4′-dicarboxylic acid) ruthenium (II) complex Is preferably 1: 2 to 2: 1 in a molar ratio, typically 1: 1 in a molar ratio.
本発明の光吸収材料の第１成分である［Ｒｕ（ｂｐｙ）３］２＋は、任意の対アニオンとの塩として、例えば［ＣｌＯ４］−、Ｃｌ−あるいはＰＦ６ −の塩として、すなわち［Ｒｕ（ｂｐｙ）３］（ＣｌＯ４）２、［Ｒｕ（ｂｐｙ）３］Ｃｌ２あるいは［Ｒｕ（ｂｐｙ）３］（ＰＦ６）２として用いられ得る。
また、本発明の光吸収材料の第２成分である［Ｒｕ（ｂｐｙ）２（ｄｃｂｐｙ）］２＋は、任意の対アニオンとの塩として、例えば［ＣｌＯ４］−、Ｃｌ−あるいはＰＦ６ −との塩として、すなわち［Ｒｕ（ｂｐｙ）２（ｄｃｂｐｙ）］（ＣｌＯ４）２、［Ｒｕ（ｂｐｙ）２（ｄｃｂｐｙ）］Ｃｌ２あるいは［Ｒｕ（ｂｐｙ）２（ｄｃｂｐｙ）］（ＰＦ６）２として用いられ得る。
[Ru (bpy) 3 ] 2+ which is the first component of the light-absorbing material of the present invention is a salt with an arbitrary counter anion, for example, a salt of [ClO 4 ] − , Cl − or PF 6 − , that is, [ It can be used as Ru (bpy) 3 ] (ClO 4 ) 2 , [Ru (bpy) 3 ] Cl 2 or [Ru (bpy) 3 ] (PF 6 ) 2 .
[Ru (bpy) 2 (dcbpy)] 2+ , which is the second component of the light-absorbing material of the present invention, is, for example, [ClO 4 ] − , Cl − or PF 6 − as a salt with any counter anion. As [Ru (bpy) 2 (dcbpy)] (ClO 4 ) 2 , [Ru (bpy) 2 (dcbpy)] Cl 2 or [Ru (bpy) 2 (dcbpy)] (PF 6 ) 2 Can be used.
前記の光吸収材料の第１成分は公知であり、購入することによりあるいはそれ自体公知の方法により合成することにより得ることができる。
また、前記の光吸収材料の第２成分は、例えば以下の工程によって得ることができる。
［Ｒｕ（ｂｐｙ）２（ｄｃｂｐｙ）］（ＰＦ６）２は、［Ｒｕ（ｂｐｙ）３］Ｃｌ２とｄｃｂｐｙとを出発原料として、アルカリ性物質の存在下、水溶液中で撹拌下に加熱した後、冷却して、水溶液を酸性として結晶を析出させ、結晶をろ過した母液を必要であれば濃縮し、ＮａＰＦ６を添加して、生成した粗［Ｒｕ（ｂｐｙ）２（ｄｃｂｐｙ）］（ＰＦ６）２を精製する工程によって得ることができる。
The first component of the light-absorbing material is known and can be obtained by purchasing or synthesizing by a method known per se.
Moreover, the 2nd component of the said light absorption material can be obtained by the following processes, for example.
[Ru (bpy) 2 (dcbpy)] (PF 6 ) 2 was heated with stirring in an aqueous solution in the presence of an alkaline substance using [Ru (bpy) 3 ] Cl 2 and dcbpy as starting materials. Upon cooling, the aqueous solution is acidified to precipitate crystals, and the mother liquor from which the crystals have been filtered is concentrated if necessary, and NaPF 6 is added to form the crude [Ru (bpy) 2 (dcbpy)] (PF 6 ) 2 can be obtained by purifying.
［Ｒｕ（ｂｐｙ）２（ｄｃｂｐｙ）］Ｃｌ２は、前記の［Ｒｕ（ｂｐｙ）２（ｄｃｂｐｙ）］（ＰＦ６）２を極性有機溶媒に溶解し、含窒素有機塩化物、例えばｎＢｕ４ＮＣｌを加えて、生成した粗［Ｒｕ（ｂｐｙ）２（ｄｃｂｐｙ）］Ｃｌ２を精製する工程によって得ることができる。
［Ｒｕ（ｂｐｙ）２（ｄｃｂｐｙ）］（ＣｌＯ４）２は、前記の［Ｒｕ（ｂｐｙ）２（ｄｃｂｐｙ）］Ｃｌ２を水に溶解させた後、ＡｇＣｌＯ４を加えて、生成した粗［Ｒｕ（ｂｐｙ）２（ｄｃｂｐｙ）］（ＣｌＯ４）２に例えば含酸素有機溶媒、例えばアセトンを加えて生成した粗［Ｒｕ（ｂｐｙ）２（ｄｃｂｐｙ）］（ＣｌＯ４）２を精製する工程によって得ることができる。
[Ru (bpy) 2 (dcbpy)] Cl 2 is obtained by dissolving the above [Ru (bpy) 2 (dcbpy)] (PF 6 ) 2 in a polar organic solvent, and adding a nitrogen-containing organic chloride such as nBu 4 NCl. In addition, the resulting crude [Ru (bpy) 2 (dcbpy)] Cl 2 can be obtained by purifying it.
[Ru (bpy) 2 (dcbpy)] (ClO 4 ) 2 is obtained by dissolving the above [Ru (bpy) 2 (dcbpy)] Cl 2 in water and then adding AgClO 4 to produce the crude [Ru Obtained by purifying crude [Ru (bpy) 2 (dcbpy)] (ClO 4 ) 2 produced by adding (bpy) 2 (dcbpy)] (ClO 4 ) 2 to, for example, an oxygen-containing organic solvent such as acetone. Can do.
本発明の前記Ｒｕ（ｂｐｙ）３］２＋および［Ｒｕ（ｂｐｙ）２（ｄｃｂｐｙ）］２＋を組み合わせた光吸収材料は、ＣＯ２還元触媒と併用することによって、光照射してＣＯ２還元性能を高くし得る。
前記のＣＯ２還元触媒としては、金属錯体、例えば、ポリフィリン、フタロシアニン
サイクラム、サレンあるいはアクエンの金属錯体、例えば前記金属が鉄、コバルト、ニッケルあるいは銀である錯体、例えばコバルトポルフィリン、鉄ポルフィリン、ニッケルサイクラム、Ａｇサイクラムなどが挙げられる。
The light-absorbing material in which the Ru (bpy) 3 ] 2+ and [Ru (bpy) 2 (dcbpy)] 2+ of the present invention are combined is used in combination with a CO 2 reduction catalyst, thereby irradiating with light to give CO 2 reduction performance. Can be high.
Examples of the CO 2 reduction catalyst include metal complexes such as polyphylline, phthalocyanine cyclam, salen or aquene metal complexes such as complexes in which the metal is iron, cobalt, nickel or silver, such as cobalt porphyrin, iron porphyrin, nickel. A cyclam, an Ag cyclam, etc. are mentioned.
本発明の光吸収材料とＣＯ２還元触媒と、好適にはさらに犠牲還元剤と組み合わせた反応系により、光照射してＣＯ２を還元する還元反応は、例えば水溶液中で行われ得る。
前記反応を実施する際に、反応器に光吸収材料とＣＯ２還元触媒と入れ、ＣＯ２を例えば水溶液に導入し、光照射下に流通式反応器を用いる連続式あるいはバッチ式に反応を行うことができる。
前記の照射光としては、特に制限はなく任意の光源、例えばキセノンランプを用いた光線であり得る。
The reduction reaction in which CO 2 is reduced by irradiation with light can be performed, for example, in an aqueous solution by a reaction system in which the light absorbing material of the present invention, a CO 2 reduction catalyst, and a sacrificial reducing agent are combined.
When carrying out the reaction, a light absorbing material and a CO 2 reduction catalyst are put into the reactor, CO 2 is introduced into an aqueous solution, for example, and the reaction is carried out continuously or batchwise using a flow reactor under light irradiation. be able to.
The irradiation light is not particularly limited and may be a light beam using an arbitrary light source such as a xenon lamp.
前記の犠牲還元剤としては、例えばメタノール、エタノールなどのアルコール類、グルコース、スクロースなどの糖類、セルロース、アスコルビン酸及びその塩、キチン、キトサン、エチレンジアミン四酢酸二ナトリウム（ＥＤＴＡ）、トリエタノールアミン、硫化物イオン等が水性溶液に溶解あるいは分散させて用いられる。犠牲還元剤は、還元触媒に光照射すると、自由電子と自由正孔が生じ、その強い還元反応により、目的とする化学物質以外に触媒それ自身が還元され、触媒作用を失う場合があるので電子供与体として機能する剤として用いられる。 Examples of the sacrificial reducing agent include alcohols such as methanol and ethanol, saccharides such as glucose and sucrose, cellulose, ascorbic acid and salts thereof, chitin, chitosan, disodium ethylenediaminetetraacetate (EDTA), triethanolamine, sulfide. Substance ions are used by dissolving or dispersing in an aqueous solution. The sacrificial reducing agent generates free electrons and free holes when light is irradiated to the reducing catalyst. Due to the strong reduction reaction, the catalyst itself may be reduced in addition to the target chemical substance, and the catalytic action may be lost. Used as an agent that functions as a donor.
本発明の光吸収材料によれば、例えば図２に示すように、光吸収材料が光を吸収して電子が励起された状態に対して、犠牲還元剤から電子が移動して光吸収材料である錯体の一電子還元種が生成する。錯体の一電子還元種の高い還元力によりＣＯ２還元触媒がＣＯに還元されることが可能となる。 According to the light-absorbing material of the present invention, for example, as shown in FIG. 2, the light-absorbing material absorbs light and the electrons are excited. A one-electron reduced species of a complex is produced. The high reducing power of the one-electron reducing species of the complex enables the CO 2 reduction catalyst to be reduced to CO.
以下、本発明の実施例を示す。
以下の実施例は単に説明するためのものであり、本発明を限定するものではない。
Examples of the present invention will be described below.
The following examples are for illustrative purposes only and are not intended to limit the invention.
以下の各例において、得られた還元触媒の評価は、発生するＣＯ等のガスを図３に示す活性評価実験系による計測システムで評価した。
また、以下の各例において、全ての試料について、ろ液のＡｇサイクラム濃度はＩＣＰにより定量した。
In each of the following examples, the obtained reduction catalyst was evaluated by measuring a generated gas such as CO with a measurement system based on an activity evaluation experimental system shown in FIG.
In each of the following examples, the concentration of Ag cyclam in the filtrate was quantified by ICP for all samples.
参考例１
１−１ Ａｇサイクラム（溶液）の合成
４０質量％のＡｇＣｌＯ４水溶液５ｇにサイクラム１ｇ、水７ｍＬを加え１時間撹拌した。析出したＡｇをろ過し、ろ液（Ａｇサイクラム溶液）を回収した。
１−２ Ａｇサイクラム＋添加剤（ＴＨＦ）の調製
４０質量％のＡｇＣｌＯ４水溶液５ｇにサイクラム１ｇ、水７ｍＬを加え１時間撹拌した。析出したＡｇをろ過し、ろ液（Ａｇサイクラム溶液）を回収した。ろ液にＴＨＦ３０ｍＬを加えた。
Reference example 1
1-1 Synthesis of Ag cyclam (solution) 1 g of cyclam and 7 mL of water were added to 5 g of 40 mass% AgClO 4 aqueous solution and stirred for 1 hour. The precipitated Ag was filtered, and the filtrate (Ag cyclam solution) was recovered.
1-2 Preparation of Ag Cyclam + Additive (THF) 1 g of cyclam and 7 mL of water were added to 5 g of 40% by mass AgClO 4 aqueous solution and stirred for 1 hour. The precipitated Ag was filtered, and the filtrate (Ag cyclam solution) was recovered. 30 mL of THF was added to the filtrate.
１−３ 光吸収材料の第２成分の合成
１）５５０ｍｇのＲｕ（ｂｐｙ）Ｃｌ２、ｄｃｂｐｙ４４４ｍｇ、ＮａＨＣＯ３５５３ｍｇ、Ｈ２Ｏ１．４ｍＬを加熱還流下に１夜撹拌後、氷冷下ｃ−Ｈ２ＳＯ４を追加してｐＨを４に調整した。晶析した結晶をろ過し、メタノール５．５ｍＬで洗浄して母液を濃縮した。濃縮残渣にＮａＰＦ６水溶液（６．９ｇのＮａＰＦ６を水３５ｍＬに溶解したもの）を添加して氷冷し、晶析した結晶をろ過・水洗した後、乾燥して７５９ｍｇの［Ｒｕ（ｂｐｙ）２（ｄｃｂｐｙ）］（ＰＦ６）２を得た。
1-3 Synthesis of Second Component of Light Absorbing Material 1) 550 mg of Ru (bpy) Cl 2 , dcbpy 444 mg, NaHCO 3 553 mg, H 2 O 1.4 mL was stirred overnight under reflux with heating, and then cooled with ice-cooled c-H 2 SO 4 was added to adjust the pH to 4. The crystallized crystals were filtered, washed with 5.5 mL of methanol, and the mother liquor was concentrated. An aqueous NaPF 6 solution (6.9 g of NaPF 6 dissolved in 35 mL of water) was added to the concentrated residue, ice-cooled, the crystallized crystals were filtered and washed with water, and then dried to obtain 759 mg of [Ru (bpy) 2 (dcbpy)] (PF 6 ) 2 was obtained.
２）５８６ｍｇの［Ｒｕ（ｂｐｙ）２（ｄｃｂｐｙ）］（ＰＦ６）２をＣＨ３ＣＮ６ｍＬに溶解し、７０５ｍｇのｎＢｕ４ＮＣｌを追加した。晶析した結晶を遠心分離し、ＣＨ３ＣＮ５ｍＬで４回洗浄し、蒸留水で溶解後、凍結乾燥して４５４ｍｇの［Ｒｕ（ｂｐｙ）２（ｄｃｂｐｙ）］Ｃｌ２を得た。 2) 586 mg of [Ru (bpy) 2 (dcbpy)] (PF 6 ) 2 was dissolved in 6 mL of CH 3 CN and 705 mg of nBu 4 NCl was added. The crystallized crystal was centrifuged, washed 4 times with 5 mL of CH 3 CN, dissolved in distilled water, and lyophilized to obtain 454 mg of [Ru (bpy) 2 (dcbpy)] Cl 2 .
３）２００ｍｇの［Ｒｕ（ｂｐｙ）２（ｄｃｂｐｙ）］Ｃｌ２をＨ２Ｏ２０ｍＬに溶解後、２８５ｍｇのＡｇＣｌＯ４を加え１時間撹拌した。副生したＡｇＣｌをろ過して除去した後、終夜減圧乾燥して１０６ｍｇの［Ｒｕ（ｂｐｙ）２（ｄｃｂｐｙ）］（ＣｌＯ４）２を得た。 3) After 200 mg of [Ru (bpy) 2 (dcbpy)] Cl 2 was dissolved in 20 mL of H 2 O, 285 mg of AgClO 4 was added and stirred for 1 hour. The by-produced AgCl was removed by filtration and then dried under reduced pressure overnight to obtain 106 mg of [Ru (bpy) 2 (dcbpy)] (ClO 4 ) 2 .
実施例１
光吸収材料の第１成分としてＲｕ（ｂｐｙ）３（ＣｌＯ４）２を用い、第２成分として［Ｒｕ（ｂｐｙ）２（ｄｃｂｐｙ）］（ＣｌＯ４）２を用いて、両成分の合計の濃度が１２５μｍｏｌ／Ｌ、２５０μｍｏｌ／Ｌ、５００μｍｏｌ／Ｌであって２成分が半々の濃度になるように水に加えて混合した。
以下の組成で反応溶液を調製した。
Example 1
Using Ru (bpy) 3 (ClO 4 ) 2 as the first component of the light-absorbing material and [Ru (bpy) 2 (dcbpy)] (ClO 4 ) 2 as the second component, the total concentration of both components Were 125 μmol / L, 250 μmol / L, and 500 μmol / L, and the two components were added to water and mixed so that the concentration was half.
A reaction solution was prepared with the following composition.
反応溶液２ｍＬの構成（実施例１、比較例１〜２）
ＣＯ２還元触媒 Ａｇサイクラム＋添加剤２５０μｍｏｌ／ｌ（水）
光吸収材料 １２５、２５０、５００μｍｏｌ／Ｌ（水）
犠牲還元剤 ４００μＬのトリエタノールアミン
溶媒 ０．２ＭのＨ３ＢＯ３−ＮａＯＨ緩衝液（ｐＨ＝１０）
Composition of 2 mL of reaction solution (Example 1, Comparative Examples 1-2)
CO 2 reduction catalyst Ag cyclam + additive 250 μmol / l (water)
Sacrificial reducing
評価方法（以下の測定はいずれも室温にて実施）
反応溶液２ｍＬを入れた１ｃｍ角の石英製セルをセプタムとビニールテープで封止した後、真空ジョイント部にセットし、気相部分を減圧・脱気した後、ＣＯ２をパージすることを３回繰り返して循環部にＣＯ２を満たした。その後、循環ポンプにより５０ｍＬ／分でＣＯ２を循環させて反応溶液を撹拌しながら約５５０Ｗ／ｍ２の光照射強度でＸｅランプにより光を照射した。照射後３０分毎にシリンジポンプにより気相部分の気体をサンプリングし、高速ＧＣに導入することでＣＯ等の成分の定量分析を行い、照射後３時間後のＣＯ発生量で反応溶液としての活性を比較した。
得られた結果を比較例の結果とまとめて図４に示す。
なお、図４におけるＴＮＣＯは、ＣＯ２還元触媒１分子当たりのＣＯ発生分子数を示す。
Evaluation method (all the following measurements are performed at room temperature)
After sealing a 1 cm square quartz cell containing 2 mL of the reaction solution with a septum and vinyl tape, set it on the vacuum joint, depressurize and degas the gas phase, and then purge CO 2 three times. filled with CO 2 to the circulation unit repeatedly. Thereafter, CO 2 was circulated at a rate of 50 mL / min with a circulation pump, and the reaction solution was stirred and irradiated with light with an Xe lamp at a light irradiation intensity of about 550 W / m 2 . Every 30 minutes after irradiation, the gas in the gas phase is sampled by a syringe pump and introduced into the high-speed GC for quantitative analysis of components such as CO. Compared.
The obtained results are summarized in FIG. 4 together with the results of the comparative example.
Note that TN CO in FIG. 4 represents the number of CO-generated molecules per molecule of the CO 2 reduction catalyst.
比較例１〜２
光吸収材料として、Ｒｕ（ｂｐｙ）３（ＣｌＯ４）２（比較例１）又は［Ｒｕ（ｂｐｙ）２（ｄｃｂｐｙ）］（ＣｌＯ４）２（比較例２）を単独で用いて、各成分の合計の濃度が１２５μｍｏｌ／Ｌ、２５０μｍｏｌ／Ｌ又は５００μｍｏｌ／Ｌとなるように、水に加えて混合した。
前記の組成で反応溶液を調製した。
得られた反応溶液により実施例１と同様に活性を評価した。
得られた結果を実施例１の結果とまとめて図４に示す。
Comparative Examples 1-2
As a light-absorbing material, Ru (bpy) 3 (ClO 4 ) 2 (Comparative Example 1) or [Ru (bpy) 2 (dcbpy)] (ClO 4 ) 2 (Comparative Example 2) is used alone. It added to water and mixed so that a total density | concentration might be 125 micromol / L, 250 micromol / L, or 500 micromol / L.
A reaction solution was prepared with the above composition.
The activity was evaluated in the same manner as in Example 1 with the obtained reaction solution.
The obtained results are shown in FIG. 4 together with the results of Example 1.
参考例２
図４から、Ｒｕ（ｂｐｙ）（ＣｌＯ４）２又は［Ｒｕ（ｂｐｙ）２（ｄｃｂｐｙ）］（ＣｌＯ４）２を単独で用いた光吸収材料に比べて、２成分を混合した光吸収材料がＣＯ発生量が多いことから、ＣＯ２還元活性が高くなっていることが理解される。
２成分の光吸収材料成分を混合することによりＣＯ２還元活性が向上した理由を考察するために、各光吸収材料の吸収スペクトルをまとめて図１に示す。
図１から、比較例２の光吸収材料（濃度：２５０μｍｏｌ／Ｌ）は、比較例１の光吸収材料（濃度：２５０μｍｏｌ／Ｌ）に比べてより長波長側の光を吸収し、混合した実施例の光吸収材料（濃度：１２５μｍｏｌ／Ｌ＋１２５μｍｏｌ／Ｌ））の場合、吸収波長が広域化していることが理解される。この結果、光エネルギーの利用効率が上り、ＣＯ２還元活性が向上したと考えられる。
Reference example 2
FIG. 4 shows that a light absorbing material in which two components are mixed is compared with a light absorbing material using Ru (bpy) (ClO 4 ) 2 or [Ru (bpy) 2 (dcbpy)] (ClO 4 ) 2 alone. It is understood that the CO 2 reduction activity is high because of the large amount of CO generated.
In order to consider the reason why the CO 2 reduction activity is improved by mixing the two light-absorbing material components, the absorption spectra of the respective light-absorbing materials are collectively shown in FIG.
From FIG. 1, the light absorbing material of Comparative Example 2 (concentration: 250 μmol / L) absorbs light on the longer wavelength side compared to the light absorbing material of Comparative Example 1 (concentration: 250 μmol / L) and is mixed. In the case of the example light absorbing material (concentration: 125 μmol / L + 125 μmol / L), it is understood that the absorption wavelength is broadened. As a result, it is considered that the utilization efficiency of light energy is increased and the CO 2 reduction activity is improved.
本発明の光吸収材料によれば、光エネルギーを有効に利用し得る光吸収波長域の広い光吸収材料を得ることができ、ＣＯ２還元触媒の存在下に光を照射して室温程度の反応温度で有用な反応性化合物であるＣＯを高い選択性で生成することを可能とし得る。 According to the light-absorbing material of the present invention, a light-absorbing material having a wide light-absorbing wavelength range in which light energy can be effectively used can be obtained, and light is irradiated in the presence of a CO 2 reduction catalyst to react at about room temperature. It may be possible to produce CO with high selectivity, a reactive compound useful at temperature.
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