JP6995334B2 - Photocatalyst and how to use it - Google Patents
Photocatalyst and how to use it Download PDFInfo
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- JP6995334B2 JP6995334B2 JP2017076377A JP2017076377A JP6995334B2 JP 6995334 B2 JP6995334 B2 JP 6995334B2 JP 2017076377 A JP2017076377 A JP 2017076377A JP 2017076377 A JP2017076377 A JP 2017076377A JP 6995334 B2 JP6995334 B2 JP 6995334B2
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- 239000011941 photocatalyst Substances 0.000 title claims description 65
- 229910052751 metal Inorganic materials 0.000 claims description 70
- 239000002184 metal Substances 0.000 claims description 70
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 40
- 150000002736 metal compounds Chemical class 0.000 claims description 38
- 150000004032 porphyrins Chemical class 0.000 claims description 27
- 239000000126 substance Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 22
- 239000001569 carbon dioxide Substances 0.000 claims description 20
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 20
- 239000003446 ligand Substances 0.000 claims description 13
- 239000012621 metal-organic framework Substances 0.000 claims description 13
- 150000004033 porphyrin derivatives Chemical class 0.000 claims description 12
- 150000002739 metals Chemical class 0.000 claims description 9
- 238000004132 cross linking Methods 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 26
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- 239000000463 material Substances 0.000 description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- 230000001699 photocatalysis Effects 0.000 description 16
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 15
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- KSPIHGBHKVISFI-UHFFFAOYSA-N Diphenylcarbazide Chemical compound C=1C=CC=CC=1NNC(=O)NNC1=CC=CC=C1 KSPIHGBHKVISFI-UHFFFAOYSA-N 0.000 description 2
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000013206 MIL-53 Substances 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
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Description
本発明は、光触媒とその使用方法に関し、特に、可視光あるいは赤外光照射により高い効率で有機物を二酸化炭素まで分解することが可能な有機金属構造体からなる光触媒とその使用方法に係る。 The present invention relates to a photocatalyst and a method of using the photocatalyst, and more particularly to a photocatalyst composed of an organic metal structure capable of decomposing an organic substance into carbon dioxide with high efficiency by irradiation with visible light or infrared light and a method of using the photocatalyst.
光照射により有害物質を分解除去する材料として光触媒材料が知られている。紫外線の量が多い屋外などでは、光触媒として酸化チタンが幅広く利用されており、それを用いて有害物質の分解が行われている。
しかし、紫外線の少ない室内では酸化チタンはその光触媒機能を十分に発揮できない。それゆえ、室内で機能する光触媒の研究が盛んにおこなわれている。
A photocatalytic material is known as a material that decomposes and removes harmful substances by light irradiation. Titanium oxide is widely used as a photocatalyst outdoors where the amount of ultraviolet rays is large, and harmful substances are decomposed by using it.
However, titanium oxide cannot fully exert its photocatalytic function in a room with little ultraviolet rays. Therefore, research on photocatalysts that function indoors is being actively conducted.
室内には紫外線は少ないが、可視光が大量に存在する。そこで、その可視光に応答する光触媒材料の開発が行われている。その例として、可視光に応答するために、酸化チタンのバンドギャップを小さくすべく窒素をドープした、窒素ドープ型酸化チタンが報告されている（特許文献1参照）。しかし、窒素ドープ型酸化チタンでも可視光の吸収量は十分ではなく、比表面積も大きくないので、その光触媒としての効率は要求を満たすものではなかった。 There is little ultraviolet light in the room, but there is a lot of visible light. Therefore, a photocatalytic material that responds to the visible light is being developed. As an example, a nitrogen-doped titanium oxide in which nitrogen is doped to reduce the band gap of titanium oxide in order to respond to visible light has been reported (see Patent Document 1). However, even with nitrogen-doped titanium oxide, the amount of visible light absorbed is not sufficient and the specific surface area is not large, so its efficiency as a photocatalyst does not meet the requirements.
また、比表面積が比較的大きく、可視光を吸収する材料として、カーボンナイトライド(Ｃ３Ｎ４)が挙げられるが、カーボンナイトライドでもバンドギャップは、非特許文献１に記載があるように、２．７ｅＶ以上であり、可視光の一部しか吸収できない。このため、より多くの可視光を吸収する材料が求められている。
Further, as a material having a relatively large specific surface area and absorbing visible light, carbon nitride (C 3N 4 ) can be mentioned. However, even in carbon nitride, the band gap is described in
可視光をよく吸収し、比表面積が大きいという２つの特性を満足する材料として、金属有機構造体（ＭＯＦ：Ｍｅｔａｌ Ｏｒｇａｎｉｃ Ｆｒａｍｅｗｏｒｋｓ）を利用した光触媒材料が近年開発されている。光触媒金属有機構造体は、無機２次元構造単位である金属化合物クラスターと有機化合物とが配位結合を通して３次元に規則的に架橋しあってできた細孔を持つ多孔体である。金属有機構造体ＭＩＬ－５３は可視光照射下で、アルコールをアルデヒドやケトンにまで選択率ほぼ１００％で酸化できると報告されている（非特許文献２参照）。一方で、このことは、アルデヒド、ケトン以上より細かくは分解できず、二酸化炭素にまで酸化できないことを示唆している。
アルデヒドやケトンは有害物であることが多く、より無害な二酸化炭素にまで酸化できなければ、環境浄化に資するとは言い難いという問題が従来の金属有機構造体を利用した光触媒にはあった。
また、特許文献２に開示されているように、可視光に比較的近い長波長の光で触媒作用を有するアンチモンポルフィリン光触媒の報告もあるが、紫外光を含む３６０ｎｍより長い波長の光を照射したときのフェノールの分解率は７１％に留まっていた。
なお、ポルフィリンを用いた光触媒としては、金属クラスターがポルフィリンで被覆された物も開示されているが、この材料はアルコール、アルデヒドなどの有害物質の吸着、分解に役立つ細孔を持っていない（特許文献３参照）。
In recent years, photocatalytic materials using metal-organic frameworks (MOFs) have been developed as materials that absorb visible light well and satisfy the two characteristics of having a large specific surface area. The photocatalytic metal-organic framework is a porous body having pores formed by regularly cross-linking a metal compound cluster, which is an inorganic two-dimensional structural unit, and an organic compound in three dimensions through a coordinate bond. It has been reported that the metal-organic framework MIL-53 can oxidize alcohols to aldehydes and ketones with a selectivity of almost 100% under visible light irradiation (see Non-Patent Document 2). On the other hand, this suggests that it cannot be decomposed more finely than aldehydes and ketones, and cannot be oxidized to carbon dioxide.
Aldehydes and ketones are often harmful substances, and if they cannot be oxidized to more harmless carbon dioxide, it is difficult to say that they will contribute to environmental purification. There was a problem with photocatalysts using conventional metal-organic structures.
Further, as disclosed in
As a photocatalyst using porphyrin, a photocatalyst in which metal clusters are coated with porphyrin is also disclosed, but this material does not have pores useful for adsorption and decomposition of harmful substances such as alcohol and aldehyde (patented). See Document 3).
以上示したように、室内光などの可視光で機能する従来の光触媒は、その比表面積が不十分であったり、可視光吸収特性が不十分であったり、酸化特性が不十分であったりと、その活性に重要な３要素をすべて満たすものではなく、可視光に対する光触媒としての効率が十分ではなかった。 As shown above, conventional photocatalysts that function with visible light such as indoor light have insufficient specific surface area, insufficient visible light absorption characteristics, and insufficient oxidation characteristics. , It did not satisfy all three important factors for its activity, and its efficiency as a photocatalyst for visible light was not sufficient.
本発明は、上記課題を解決し、可視光から赤外光に対しより高い効率で、有機物を二酸化炭素を含む炭素含有物質にまで酸化分解できる光触媒を提供することを目的とする。また、可視光から赤外光に対しより高い効率で、有機物を、二酸化炭素を含む炭素含有物質あるいは二酸化炭素にまで酸化分解できる光触媒の使用方法を提供することを目的とする。
より詳しく言うと、本発明は、可視から赤外領域の幅広い光に対する光吸収が強く、有機物を吸着する比表面積が大きく、有機物、とりわけアルコールなどの有害な有機物を、二酸化炭素を含む有害性の低い炭素含有物質あるいは二酸化炭素にまで酸化分解する金属有機構造体光触媒およびその光触媒の使用方法を提供することを目的とする。
An object of the present invention is to solve the above-mentioned problems and to provide a photocatalyst capable of oxidatively decomposing an organic substance into a carbon-containing substance containing carbon dioxide with higher efficiency from visible light to infrared light. Another object of the present invention is to provide a method for using a photocatalyst capable of oxidatively decomposing an organic substance into a carbon-containing substance containing carbon dioxide or carbon dioxide with higher efficiency from visible light to infrared light.
More specifically, the present invention has strong light absorption to a wide range of light in the visible to infrared region, has a large specific surface area for adsorbing organic substances, and is harmful to organic substances, especially harmful organic substances such as alcohol, including carbon dioxide. It is an object of the present invention to provide a metal organic structure photocatalyst that oxidatively decomposes to a low carbon-containing substance or carbon dioxide, and a method for using the photocatalyst.
本発明者らは上記の状況を顧みて、試行錯誤を重ねて検討を行った。その結果、金属有機構造体の架橋配位子に金属ポルフィリン、特に鉄ポルフィリン、銅ポルフィリン、ニッケルポルフィリン、コバルトポルフィリン、マンガンポルフィリンの何れか1つ以上の金属ポルフィリンを用いることにより、光照射により生じた電子、ホールといったキャリアの再結合を抑え、光触媒活性を高め、さらには有害な有機物を二酸化炭素にまで酸化分解できることを見出し、本発明を完成させた。
本発明の構成を下記に示す。
（構成１）
金属化合物クラスターと金属ポルフィリンを含む金属有機構造体であって、
前記金属化合物クラスターは無機２次元構造単位としてＺｒ金属化合物を含み、
前記金属ポルフィリンは前記金属化合物クラスターの架橋配位子になっており、
前記金属ポルフィリンの金属は、Ｆｅ３＋，Ｆｅ２＋の少なくとも何れか１以上である、光触媒。
（構成２）
金属化合物クラスターと金属ポルフィリン誘導体を含む金属有機構造体であって、
前記金属化合物クラスターは無機２次元構造単位としてＺｒ金属化合物を含み、
前記金属ポルフィリン誘導体は前記金属化合物クラスターの架橋配位子になっており、
前記金属ポルフィリン誘導体の金属は、Ｆｅ３＋，Ｆｅ２＋の少なくとも何れか１以上である、光触媒。
（構成３）
前記金属ポルフィリンまたは前記金属ポルフィリン誘導体の金属サイトが、前記金属ポルフィリンまたは前記金属ポルフィリン誘導体の金属で全て埋められている、構成１または２記載の光触媒。
（構成４）
前記金属ポルフィリンまたは前記金属ポルフィリン誘導体の金属サイトの一部が、前記金属ポルフィリンまたは前記金属ポルフィリン誘導体の金属以外の物質に置き換わっている、あるいは欠損している、構成１から３の何れか１記載の光触媒。
（構成５）
前記金属化合物クラスターは、μ３を３個の金属に架橋していることを表すとして、Ｚｒ６（μ３－Ｏ）４（μ３－ＯＨ）４（ＯＨ）６（ＯＨ２）６（ＣＯＯ－）６またはＺｒ６（μ３－ＯＨ）８（ＯＨ）８である、構成１から４の何れか１記載の光触媒。
（構成６）
有機物を二酸化炭素に酸化分解する、構成１から５の何れか１記載の光触媒。
（構成７）
有害金属をより無害化する、構成１から５の何れか１記載の光触媒。
（構成８）
構成１から７の何れか１記載の光触媒に可視光を照射する、光触媒の使用方法。
（構成９）
構成１から７の何れか１記載の光触媒に赤外光を照射する、光触媒の使用方法。
（構成１０）
構成１から７の何れか１記載の光触媒に可視光および赤外光を照射する、光触媒の使用方法。
The present inventors have conducted trial and error in consideration of the above situation. As a result, by using metal porphyrin, particularly iron porphyrin, copper porphyrin, nickel porphyrin, cobalt porphyrin, manganese porphyrin, one or more metal porphyrins as the bridging ligand of the metal-organic framework, it was generated by light irradiation. We have found that the recombination of carriers such as electrons and holes can be suppressed, the photocatalytic activity can be enhanced, and harmful organic substances can be oxidatively decomposed into carbon dioxide, and the present invention has been completed.
The configuration of the present invention is shown below.
(Structure 1)
A metal-organic framework containing metal compound clusters and metal porphyrins.
The metal compound cluster contains a Zr metal compound as an inorganic two-dimensional structural unit and contains.
The metal porphyrin serves as a cross-linking ligand for the metal compound cluster, and is used as a cross-linking ligand.
A photocatalyst in which the metal of the metal porphyrin is at least one of Fe 3+ and Fe 2+ .
(Structure 2)
A metal-organic framework containing a metal compound cluster and a metal porphyrin derivative.
The metal compound cluster contains a Zr metal compound as an inorganic two-dimensional structural unit and contains.
The metal porphyrin derivative serves as a cross-linking ligand for the metal compound cluster.
A photocatalyst in which the metal of the metal porphyrin derivative is at least one of Fe 3+ and Fe 2+ .
(Structure 3)
The photocatalyst according to
(Structure 4)
13. photocatalyst.
(Structure 5)
Zr 6 (μ 3 -O) 4 (μ 3 -OH) 4 (OH) 6 (OH 2 ) 6 (COO), assuming that μ 3 is cross-linked to three metals in the metal compound cluster. - ) 6 or Zr 6 (μ 3 -OH) 8 (OH) 8 according to any one of
(Structure 6)
The photocatalyst according to any one of
(Structure 7)
The photocatalyst according to any one of
(Structure 8)
A method for using a photocatalyst, which irradiates the photocatalyst according to any one of
(Structure 9)
A method for using a photocatalyst, which irradiates the photocatalyst according to any one of
(Structure 10)
A method for using a photocatalyst, which irradiates the photocatalyst according to any one of
本発明の光触媒金属有機構造体は、可視光および赤外光を強く吸収する多孔体光触媒であり、１０００ｍ２ｇ－１以上の大きな比表面積を持ち、可視光照射下で強い酸化力を持つ光触媒である。このため、本発明により、可視光から赤外光を含む幅広い波長域の光により高い効率で、有害な有機物を含む有機物を、二酸化炭素または二酸化炭素を含む炭素含有物質にまで酸化分解できる光触媒、およびその使用方法を提供することができる。 The photocatalyst metal-organic framework of the present invention is a porous photocatalyst that strongly absorbs visible light and infrared light, has a large specific surface area of 1000 m 2 g -1 or more, and has a strong oxidizing power under visible light irradiation. Is. Therefore, according to the present invention, a photocatalyst capable of oxidatively decomposing an organic substance containing harmful organic substances into carbon dioxide or a carbon-containing substance containing carbon dioxide with high efficiency by light in a wide wavelength range including visible light to infrared light. And its usage can be provided.
以下本発明を実施するための形態を、図面を参照しながら説明する。 Hereinafter, embodiments for carrying out the present invention will be described with reference to the drawings.
（実施の形態１）
本発明の有機金属構造体光触媒は、図１に示すように無機２次元構造単位としてＺｒ（ＯＨ）６などを含んだ金属化合物クラスター１１に金属ポルフィリン１２が架橋して配位することでできた多孔体である。その具体例としては、ＰＣＮ（Ｐｏｒｏｕｓ Ｃｏｏｒｄｉｎａｔｉｏｎ Ｎｅｔｗｏｒｋ）－２２４、ＰＣＮ－２２２、ＭＭＰＦ（Ｍｅｔａｌ‐Ｍｅｔａｌｌｏｐｏｒｐｈｙｒｉｎ Ｆｒａｍｅｗｏｒｋ）－１などが挙げられる。
金属化合物クラスターの金属化合物としては、金属ポルフィリンと安定な多孔体を作ればどのような金属化合物でもよく、ジルコニウム（Ｚｒ）金属化合物、ハフニウム（Ｈｆ）金属化合物、チタン（Ｔｉ）金属化合物、鉄（Ｆｅ）金属化合物、ニッケル（Ｎｉ）金属化合物、マンガン（Ｍｎ）金属化合物、ゲルマニウム（Ｇｅ）金属化合物、シリコン（Ｓｉ）金属化合物、スズ（Ｓｎ）金属化合物などを挙げることができる。これらの中でも、Ｚｒ金属化合物、Ｈｆ金属化合物、Ｔｉ金属化合物、Ｎｉ金属化合物およびＭｎ金属化合物は安定であり、好ましい。無機２次元構造単位である金属化合物クラスターの具体例としては、Ｚｒ６（μ３－Ｏ）４（μ３－ＯＨ）４（ＯＨ）６（ＯＨ２）６（ＣＯＯ－）６、Ｚｒ６（μ３－ＯＨ）８（ＯＨ）８などが挙げられる。ここで、μ３は３個の金属に架橋していることを表す。
(Embodiment 1)
As shown in FIG. 1, the metal-organic framework photocatalyst of the present invention was formed by coordinating a metal-
The metal compound of the metal compound cluster may be any metal compound as long as it forms a stable porous body with metal porphyrin, and is a zirconium (Zr) metal compound, a hafnium (Hf) metal compound, a titanium (Ti) metal compound, and iron ( Examples thereof include Fe) metal compounds, nickel (Ni) metal compounds, manganese (Mn) metal compounds, germanium (Ge) metal compounds, silicon (Si) metal compounds, tin (Sn) metal compounds and the like. Among these, Zr metal compounds, Hf metal compounds, Ti metal compounds, Ni metal compounds and Mn metal compounds are stable and preferable. Specific examples of the metal compound cluster, which is an inorganic two-dimensional structural unit, include Zr 6 (μ 3 -O) 4 (μ 3 -OH) 4 (OH) 6 (OH 2 ) 6 ( COO- ) 6 , Zr 6 ( μ 3 -OH) 8 (OH) 8 and the like can be mentioned. Here, μ 3 indicates that the metal is crosslinked with three metals.
金属ポルフィリンを構成するポルフィリンは特に制約はなく、例えば、テトラキス（４－カルボキシフェニル）ポルフィリン、テトラ（４－ピリジル）ポルフィリン、ディカルボキシフェニルポルフェリンなどを挙げることができる。 The porphyrin constituting the metal porphyrin is not particularly limited, and examples thereof include tetrakis (4-carboxyphenyl) porphyrin, tetra (4-pyridyl) porphyrin, and dicarboxyphenyl porphyrin.
金属ポルフィリンに利用できる金属（金属イオン）としては、可視光から赤外光の領域の光を強く吸収し、酸化分解力を高めるという観点から、Ｆｅ３＋，Ｆｅ２＋，Ｃｕ＋，Ｃｕ２＋，Ｃｏ２＋，Ｃｏ３＋，Ｍｎ２＋，Ｍｎ４＋，Ｍｎ７＋が特に好ましい。また、ここに挙げた金属は混合原子価をもち、金属イオン自身の酸化、還元、再酸化、再還元の一連のプロセスが容易で、光触媒の耐久性を高める上でも有効である。また、これらの金属は非白色の有色の金属イオンであり、このことにより可視光および赤外光の吸収を高めることができる。
なお、半金属であるアンチモン（Ｓｂ）を用いた場合は、Ｓｂ５＋イオンを含むＮａＳｂＯ３が白色あるいは無色を示すように、可視光域の光吸収能を殆ど増強できず、有機物を効率的には分解できない。
Metals (metal ions) that can be used for metallic porphyrin include Fe 3+ , Fe 2+ , Cu + , Cu 2+ , and Co from the viewpoint of strongly absorbing light in the visible to infrared light region and enhancing oxidative decomposition power. 2+ , Co 3+ , Mn 2+ , Mn 4+ , and Mn 7+ are particularly preferable. In addition, the metals listed here have mixed valences, and a series of processes of oxidation, reduction, reoxidation, and rereduction of the metal ion itself is easy, and it is also effective in improving the durability of the photocatalyst. In addition, these metals are non-white colored metal ions, which can enhance the absorption of visible and infrared light.
When antimony (Sb), which is a metalloid, is used, the light absorption capacity in the visible light region can hardly be enhanced so that NaSbO 3 containing Sb5 + ions is white or colorless, and organic substances can be efficiently produced. Cannot be disassembled.
また、金属ポルフィリンは、その金属が配置される金属サイトがその金属ポルフィリンの金属で全て埋められている状態が好ましいが、金属ポルフィリンの金属サイトの一部がディフェクトとなっている状態、すなわち、ポルフィリンと金属ポルフィリンが併存している状態でも用いることができる。 Further, in the metal porphyrin, it is preferable that the metal site on which the metal is placed is completely filled with the metal of the metal porphyrin, but a part of the metal site of the metal porphyrin is defective, that is, porphyrin. It can also be used in the state where and metal porphyrin coexist.
また、金属ポルフィリンの代わりに金属ポルフィリン誘導体を用いることもできる。金属ポルフィリン誘導体としては、例えばコロール、フタロシアニン、クロリンなどを挙げることができる。 Further, a metal porphyrin derivative can be used instead of the metal porphyrin. Examples of the metal porphyrin derivative include corrole, phthalocyanine, and chlorin.
また、本発明の光触媒は、酸化チタンや酸化タングステンといった他の光触媒と併用して利用してもよい。すなわち紫外光領域で高活性な酸化チタンと本発明の有機金属構造体光触媒のハイブリットにして利用してもよい。 Further, the photocatalyst of the present invention may be used in combination with other photocatalysts such as titanium oxide and tungsten oxide. That is, it may be used as a hybrid of titanium oxide having high activity in the ultraviolet light region and the photocatalyst of the organic metal structure of the present invention.
本発明の有機金属構造体光触媒は、紫外光、可視光、赤外光に強い吸収を持つので、紫外光が豊富にある屋外のみならず、紫外光は少ないが可視光は十分にある屋内でも、様々な有機物を酸化分解することができる。さらには、本発明の光触媒では、有機物の酸化は、反応中間体生成までではなく、最終酸化生成物である二酸化炭素にまで分解するほど強い酸化力を持つ。その極めて強い酸化分解力を用いることで様々な機能を得ることができる。
例えば、汚れ防止効果や悪臭の防止、汚染した空気の清浄、殺菌、抗菌、セルフクリーニング効果など様々な用途に利用できる。
Since the organic metal structure photocatalyst of the present invention has strong absorption of ultraviolet light, visible light, and infrared light, it is not only outdoors where ultraviolet light is abundant, but also indoors where ultraviolet light is small but visible light is sufficient. , Various organic substances can be oxidatively decomposed. Furthermore, in the photocatalyst of the present invention, the oxidation of organic substances has such a strong oxidizing power that it decomposes not only to the formation of reaction intermediates but also to carbon dioxide, which is the final oxidation product. Various functions can be obtained by using the extremely strong oxidative decomposition power.
For example, it can be used for various purposes such as antifouling effect, prevention of bad odor, cleaning of contaminated air, sterilization, antibacterial effect, and self-cleaning effect.
さらに、本発明の光触媒は有機化合物と金属化合物のハイブリット材料なので、様々な材料と親和性が優れるように調製することができる。様々な材料表面にスパッタや塗布などにより本発明の光触媒をコーティングすることで、その面に上記に示した機能を付与することが可能になる。 Furthermore, since the photocatalyst of the present invention is a hybrid material of an organic compound and a metal compound, it can be prepared so as to have an excellent affinity with various materials. By coating the surface of various materials with the photocatalyst of the present invention by sputtering, coating, or the like, it becomes possible to impart the functions shown above to the surface thereof.
以下に示す本発明の実施例においては、有機金属構造体光触媒は粉末状であるが、ＰＬＤ（Ｐｕｌｓｅｄ Ｌａｓｅｒ Ｄｅｐｏｓｉｔｉｏｎ）やスパッタリング装置などにより、素材表面に蒸着することで薄膜での形成が可能であり、上記目的に供することができる。また、この粉末を溶媒に溶かしてゾルあるいは分散させてスラリーにすることによっても薄膜にすることができる。 In the examples of the present invention shown below, the organic metal-organic framework photocatalyst is in the form of powder, but it can be formed into a thin film by depositing it on the surface of the material by PLD (Pulsed Laser Deposition), a sputtering device, or the like. , Can be used for the above purpose. A thin film can also be formed by dissolving this powder in a solvent and making it into a sol or a slurry to form a slurry.
なお、ここに挙げた機能性や用途は本発明の効果などの一部を述べているのにすぎず、様々な用途に利用できる。本発明の実施形態である光触媒材料およびその製造方法は上記実施形態に限定されるものではなく、本発明の技術的思想の範囲内で、変更して用いることもできる。本実施形態の具体例を以下の実施例を用いて示すが、本発明はこれらの実施例に限定されるものではない。 It should be noted that the functionality and uses listed here are only a part of the effects of the present invention and can be used for various purposes. The photocatalyst material and the method for producing the photocatalyst material according to the embodiment of the present invention are not limited to the above-described embodiment, and may be modified and used within the scope of the technical idea of the present invention. Specific examples of the present embodiment will be shown using the following examples, but the present invention is not limited to these examples.
（実施例１）
鉄ポルフィリンを配位子としたジルコニウム（Ｚｒ）化合物を用いた有機金属構造体（Ｆｅ－ＰＣＮ－２２４）を以下に示す方法を用いて合成した。
１２０ｍｇのＺｒＯＣｌ２・８Ｈ２Ｏを５０ｍＬのジメチルホルムアミド（ＤＭＦ）中で撹拌後、そこに２５ｍｇのテトラキス（４－カルボキシフェニル）ポルフィリンと１２．５ｍＬの酢酸を加えた。その溶液を密閉容器内で３３８Ｋの温度で３日間熱処理することで粉末を得た（ソルボサーマル合成）。その粉末を洗浄後、塩化鉄で処理することで有機金属構造体（Ｆｅ－ＰＣＮ－２２４）を合成した。
その構造の模式図を図１に示す。ここで、同図の（ａ）は全体の構造を、（ｂ）はその中の架橋配位子の部分の構造を示す。Ｍは金属を表し、実施例１の場合Ｆｅである。その周りに配置された４つの大きい球は窒素、その周りの中くらいの球は炭素、小さい球は水素を表し、最外部の４カ所計８個の大きな球は酸素を表す。１つのＺｒ化合物無機２次元構造単位に６つのポルフィリンが配位した構造をしている。作製した試料がこの構造になることは、ＸＲＤ（Ｘ－ｒａｙ Ｄｉｆｆｒａｃｔｉｏｎ）によって確認した。
(Example 1)
An organic metal structure (Fe-PCN-224) using a zirconium (Zr) compound having iron porphyrin as a ligand was synthesized by the method shown below.
After stirring 120 mg of ZrOCl 2.8H 2 O in 50 mL of dimethylformamide (DMF), 25 mg of tetrakis (4-carboxyphenyl) porphyrin and 12.5 mL of acetic acid were added thereto. The solution was heat-treated in a closed container at a temperature of 338 K for 3 days to obtain a powder (solvothermal synthesis). After washing the powder, it was treated with iron chloride to synthesize an organic metal structure (Fe-PCN-224).
A schematic diagram of the structure is shown in FIG. Here, (a) of the figure shows the whole structure, and (b) shows the structure of the part of the cross-linking ligand in it. M represents a metal and is Fe in the case of Example 1. The four large spheres arranged around it represent nitrogen, the medium spheres around them represent carbon, the small spheres represent hydrogen, and the four outermost four large spheres represent oxygen. It has a structure in which six porphyrins are coordinated to one Zr compound inorganic two-dimensional structural unit. It was confirmed by XRD (X-ray Diffraction) that the prepared sample had this structure.
この試料の光吸収特性を評価した。その結果を図２に示す。
この試料（Ｆｅ－ＰＣＮ－２２４）は、波長４００ｎｍ以上の可視光に対して強い吸収を示し、赤外線領域の波長８００ｎｍ以上の光に対しても吸収を示した。このようにこの試料は可視光域全域の光を吸収する。
また、比表面積を比表面積・細孔分布測定装置（ＢｅｌｓｏｒｐＩＩ、日本ベル社製）を用いて７７Ｋでの窒素吸着法で測定したところ、その値は約１６９０ｍ２・ｇ－１であり、高い比表面積を示した。
The light absorption characteristics of this sample were evaluated. The results are shown in FIG.
This sample (Fe-PCN-224) showed strong absorption to visible light having a wavelength of 400 nm or more, and also showed absorption to light having a wavelength of 800 nm or more in the infrared region. In this way, this sample absorbs light in the entire visible light region.
Moreover, when the specific surface area was measured by the nitrogen adsorption method at 77K using a specific surface area / pore distribution measuring device (BelsorpII, manufactured by Nippon Bell Co., Ltd.), the value was about 1690 m 2 · g -1 , which is a high ratio. The surface area is shown.
次に可視光照射下での光触媒活性の評価を行った。その結果を図３に示す。
ここでの光触媒活性は以下の方法により評価した。
５００ｃｍ３の反応容器に上記試料５０ｍｇ（面積８．５ｃｍ２）を入れ、密閉した後、２－プロパノールガスをその反応容器に入れた。その後、暗所で数時間保持して吸着脱離平衡状態になったことを確認後、可視光を照射した。その後、生成したガスをＦＩＤ（Ｆｌａｍｅ Ｉｏｎｉｚａｔｉｏｎ Ｄｅｔｅｃｔｏｒ）検出器、メタナイザー付きガスクロマトグラフィーを用いて定量した。なお、可視光照射には３００Ｗのキセノンランプと紫外光カットフィルターを利用した。
Next, the photocatalytic activity under visible light irradiation was evaluated. The results are shown in FIG.
The photocatalytic activity here was evaluated by the following method.
50 mg (area 8.5 cm 2 ) of the above sample was placed in a 500 cm 3 reaction vessel, sealed, and then 2-propanol gas was placed in the reaction vessel. After that, it was held in a dark place for several hours to confirm that it was in an equilibrium state of adsorption and desorption, and then irradiated with visible light. Then, the generated gas was quantified using a FID (Flame Ionization Detector) detector and gas chromatography with a metanizer. A 300 W xenon lamp and an ultraviolet light cut filter were used for visible light irradiation.
２－プロパノールを酸化分解すると、まず反応中間体としてアセトンが生成するので、そのアセトンの生成量について評価した。アセトンの生成量はほぼ光照射時間に比例して増加し、４時間光照射後には１０００ｐｐｍを超える大量のアセトンが検出された。このことはこの光触媒材料が高活性であることを示している。また、反応は擬０次反応で進行し、その反応速度は２８０ｐｐｍ・ｈ‐１と見積もられた。同時に最終生成物である二酸化炭素の増加も検出され、表１に示すようにその反応速度は３．７ｐｐｍ・ｈ‐１であった。有意に二酸化炭素の増大も見られることから、この光触媒は強い酸化力を持つ光触媒である。 When 2-propanol is oxidatively decomposed, acetone is first produced as a reaction intermediate, and the amount of acetone produced was evaluated. The amount of acetone produced increased substantially in proportion to the light irradiation time, and after 4 hours of light irradiation, a large amount of acetone exceeding 1000 ppm was detected. This indicates that this photocatalytic material is highly active. The reaction proceeded as a pseudo-zero-order reaction, and the reaction rate was estimated to be 280 ppm · h -1 . At the same time, an increase in carbon dioxide, which is the final product, was also detected, and the reaction rate was 3.7 ppm · h -1 as shown in Table 1. This photocatalyst is a photocatalyst with strong oxidizing power because a significant increase in carbon dioxide is also observed.
次に光触媒の耐久性を評価した（図４）。
上記作製した試料（Ｆｅ－ＰＣＮ－２２４）に対して光を４時間照射後、反応容器内を純空気（清浄度の高い乾燥空気）で置換して反応容器内のアセトン量を０ｐｐｍにした後、再度２－プロパノールを加え、４時間光照射するという一連の実験を繰り返すことで耐久性の評価を行った。
その結果、図４に示されるように、繰り返し実験を行ってもアセトンの生成速度に低下は見られず、実施例１で作製した光触媒は活性を維持した。したがって、この材料は高い耐久性を持っていることが確認された。
Next, the durability of the photocatalyst was evaluated (Fig. 4).
After irradiating the prepared sample (Fe-PCN-224) with light for 4 hours, the inside of the reaction vessel is replaced with pure air (dry air with high cleanliness) to reduce the amount of acetone in the reaction vessel to 0 ppm. , 2-Propanol was added again, and the durability was evaluated by repeating a series of experiments of irradiating with light for 4 hours.
As a result, as shown in FIG. 4, no decrease in the production rate of acetone was observed even after repeated experiments, and the photocatalyst produced in Example 1 maintained its activity. Therefore, it was confirmed that this material has high durability.
（実施例２）
さらに、この試料の６価クロムの毒性低下実験によっても光触媒特性を評価した。６価クロムとしてはＫ２Ｃｒ２０７を用い、反応容器に試料５ｍｇと６０ｍＬの６価クロム水溶液（６価クロム濃度：１６ｐｐｍ）を入れ、吸着平衡状態を確認後３００Ｗキセノンライトと紫外光カットフィルターを用いて可視光を照射することで光触媒活性を評価した。なお、水溶液にはシュウ酸５ｍｇを添加してｐＨを３にコントロールした。また、６価クロムは、ＤＰＣ（Ｄｉｐｈｅｎｙｌｃａｒｂａｚｉｄｅ）法を用いて発色させ、波長５４２ｎｍにおける吸光度を紫外可視分光光度計で測定することで定量化した。
(Example 2)
Furthermore, the photocatalytic properties were evaluated by the toxicity reduction experiment of hexavalent chromium of this sample. K2Cr207 is used as hexavalent chromium, 5 mg of sample and 60 mL of hexavalent chromium aqueous solution (hexavalent chromium concentration: 16 ppm) are placed in a reaction vessel, and after confirming the adsorption equilibrium state, visible using 300 W xenone light and an ultraviolet light cut filter. The photocatalytic activity was evaluated by irradiating with light. The pH of the aqueous solution was controlled to 3 by adding 5 mg of oxalic acid. Hexavalent chromium was quantified by developing a color using a DPC (Diphenylcarbazide) method and measuring the absorbance at a wavelength of 542 nm with an ultraviolet-visible spectrophotometer.
吸着平衡後の６価クロムの量をＣ０、光照射により光触媒反応処理を行っているときの量をＣとして６価クロム量の吸着平衡後の初期値との比（Ｃ／Ｃ０）を得られたデータでプロットすると、可視光照射により急激に６価クロムの量が減少していることがわかる（図５）。そして、わずか４０分でほぼすべての６価クロムをより有害性の低い３価クロムに変換できた。 The ratio (C / C 0 ) of the amount of hexavalent chromium to the initial value after adsorption equilibrium is defined as C 0 for the amount of hexavalent chromium after adsorption equilibrium and C for the amount when photocatalytic reaction treatment is performed by light irradiation. When plotted with the obtained data, it can be seen that the amount of hexavalent chromium is rapidly reduced by the irradiation with visible light (Fig. 5). And in just 40 minutes, almost all hexavalent chromium could be converted to less harmful trivalent chromium.
（実施例３）
鉄ポルフィリンを配位子としたＺｒ化合物を用いた有機金属構造体（Ｆｅ－ＰＣＮ－２２２）を以下に示す方法を用いて合成した。
７５ｍｇのＺｒＯＣｌ２・８Ｈ２Ｏを２０ｍＬのジメチルホルムアミド（ＤＭＦ）中で撹拌後、そこに１３ｍｇのテトラキス（４－カルボキシフェニル）ポルフィリンと１４ｍＬの蟻酸を加えた。その溶液を密閉容器内で４０３Ｋの温度で熱処理することで粉末を得た。その粉末を洗浄後、塩化鉄で処理することで有機金属構造体（Ｆｅ－ＰＣＮ－２２２）を合成した。
(Example 3)
An organic metal structure (Fe-PCN-222) using a Zr compound having iron porphyrin as a ligand was synthesized by the method shown below.
After stirring 75 mg of ZrOCl 2.8H 2 O in 20 mL of dimethylformamide (DMF), 13 mg of tetrakis (4-carboxyphenyl) porphyrin and 14 mL of formic acid were added thereto. The solution was heat treated in a closed container at a temperature of 403 K to obtain a powder. After washing the powder, it was treated with iron chloride to synthesize an organic metal structure (Fe-PCN-222).
次に、可視光照射下での光触媒活性の評価を行った。その結果を図６に示す。
活性評価は、実施例１の活性評価法と同様の方法で評価した。
その結果、アセトンの生成量は４時間光照射後約１０００ｐｐｍとなり、この実施例３の材料も活性の高い材料であることがわかった。
Next, the photocatalytic activity under visible light irradiation was evaluated. The results are shown in FIG.
The activity was evaluated by the same method as the activity evaluation method of Example 1.
As a result, the amount of acetone produced was about 1000 ppm after light irradiation for 4 hours, and it was found that the material of Example 3 was also a highly active material.
（比較例１）
鉄を含まないポルフィリンを配位子としたＺｒ化合物を用いた有機金属構造体（Ｆｅ－ＰＣＮ－２２４）を以下に示す方法を用いて合成した。
１２０ｍｇのＺｒＯＣｌ２・８Ｈ２Ｏを５０ｍＬのジメチルホルムアミド（ＤＭＦ）中で撹拌後、そこに２５ｍｇのテトラキス（４－カルボキシフェニル）ポルフィリンと１２．５ｍＬの酢酸を加えた。その溶液を密閉容器内で３３８Ｋの温度で３日間熱処理することで粉末を得た。その粉末を洗浄することで、比較例１のＰＣＮ－２２４サンプルを得た。その比表面積は約２２７０ｍ２・ｇ－１と高い表面積を示した。
(Comparative Example 1)
An organic metal structure (Fe-PCN-224) using a Zr compound having iron-free porphyrin as a ligand was synthesized by the method shown below.
After stirring 120 mg of ZrOCl 2.8H 2 O in 50 mL of dimethylformamide (DMF), 25 mg of tetrakis (4-carboxyphenyl) porphyrin and 12.5 mL of acetic acid were added thereto. The solution was heat-treated in a closed container at a temperature of 338 K for 3 days to obtain a powder. By washing the powder, a PCN-224 sample of Comparative Example 1 was obtained. Its specific surface area was as high as about 2270 m 2 · g -1 .
その試料の活性を実施例１の活性評価法と同様の方法で評価した。
その結果、アセトンの生成は確認できたが、４時間で生成したアセトンの量は１５０ｐｐｍにも満たず、そのアセトンの生成速度は３２ｐｐｍ・ｈ‐１と実施例１、３と比べてはるかに低いものであった（図３）。二酸化炭素の生成速度も０．４ｐｐｍ・ｈ‐１と微量で、有意な二酸化炭素の生成は確認できなかった（表１）。すなわち、比較例１のサンプルの酸化力は弱いことがわかった。
The activity of the sample was evaluated by the same method as the activity evaluation method of Example 1.
As a result, the production of acetone was confirmed, but the amount of acetone produced in 4 hours was less than 150 ppm, and the rate of production of acetone was 32 ppm · h -1 which was much lower than that of Examples 1 and 3. It was a thing (Fig. 3). The carbon dioxide production rate was as small as 0.4 ppm · h -1 , and no significant carbon dioxide production was confirmed (Table 1). That is, it was found that the oxidizing power of the sample of Comparative Example 1 was weak.
作製した材料の光吸収スペクトルを比較した図２からわかるように、比較例１の光吸収は、実施例１に比べ、特に波長４００ｎｍ以上５００ｎｍ以下、および６００ｎｍ以上の光に対して約４割吸収が少ない。言い換えれば、鉄ポルフォリンを用いた実施例１の光触媒は、鉄を含まないポルフォリンを用いた比較例１より光吸収が約４割大きい。一方で、有機物の分解量は、表１に示されるように、実施例１が比較例１より桁違いに大きい。鉄ポルフォリンを用いることにより、光吸収を大幅に上回る光触媒効率が得られることが分かる。 As can be seen from FIG. 2 comparing the light absorption spectra of the prepared materials, the light absorption of Comparative Example 1 is about 40% higher than that of Example 1, especially for light having a wavelength of 400 nm or more and 500 nm or less, and 600 nm or more. Less is. In other words, the photocatalyst of Example 1 using iron porphorin has about 40% greater light absorption than Comparative Example 1 using iron-free porphorin. On the other hand, as shown in Table 1, the amount of decomposition of the organic substance in Example 1 is an order of magnitude larger than that in Comparative Example 1. It can be seen that by using iron porphorin, photocatalytic efficiency significantly exceeding that of light absorption can be obtained.
実施例１と比較例１の両試料のフォトルミネッセンス（光発光）を、蛍光分光装置（日本分光製）を用いて測定した。その結果を図７に示すが、発光のピークが比較例１の方が大きく、より比較例１の方が光照射で生じた電子とホールが再結合しやすいことがわかる。電子とホールが再結合しやすいと、光触媒反応に利用される電子、ホール量が減るため、光触媒活性が低くなりやすくなる。 The photoluminescence (light emission) of both the samples of Example 1 and Comparative Example 1 was measured using a fluorescence spectroscope (manufactured by Nippon Spectroscopy). The results are shown in FIG. 7, and it can be seen that the peak of light emission is larger in Comparative Example 1, and that the electrons and holes generated by light irradiation are more likely to recombine in Comparative Example 1. When electrons and holes are easily recombined, the amount of electrons and holes used in the photocatalytic reaction is reduced, so that the photocatalytic activity tends to be low.
以上述べてきたように、金属ポルフォリン（鉄ポルフォリン）を用いることと、その金属ポルフォリンを架橋配位子として金属化合物クラスターに組みことの両者の相乗効果によって、このような高い光触媒効率と二酸化炭素にまで分解できる強い酸化力が得られた。 As described above, the synergistic effect of using metal porphorin (iron porforin) and assembling the metal porphorin into a metal compound cluster as a bridging ligand results in such high photocatalytic efficiency and carbon dioxide. A strong oxidizing power that can be decomposed was obtained.
（比較例２）
さらに、この試料の６価クロムの毒性低下実験によっても光触媒特性を評価した。その活性の評価方法は実施例２と同じ方法を用いた。可視光照射により６価クロムの量が減少するが、４０分の光照射でわずか２０～３０％の６価クロムしか削減処理できなかった（図５）。実施例２の材料は同じ時間の光照射でほぼすべて処理できていることから、実施例２の試料（Ｆｅ－ＰＣＮ－２２４）は優れた有害金属の毒性を低下させる能力のある材料であるといえる。
(Comparative Example 2)
Furthermore, the photocatalytic properties were evaluated by the toxicity reduction experiment of hexavalent chromium of this sample. The same method as in Example 2 was used for the evaluation method of the activity. Although the amount of hexavalent chromium was reduced by irradiation with visible light, only 20 to 30% of hexavalent chromium could be reduced by irradiation with light for 40 minutes (Fig. 5). Since almost all of the materials of Example 2 could be treated by irradiation with light for the same time, the sample of Example 2 (Fe-PCN-224) is considered to be a material capable of reducing the toxicity of excellent harmful metals. I can say.
（比較例３）
鉄を含まないポルフィリンを配位子としたＺｒ化合物を用いた有機金属構造体（ＰＣＮ－２２２）を以下に示す方法を用いて合成した。
７５ｍｇのＺｒＯＣｌ２・８Ｈ２Ｏを２０ｍＬのジメチルホルムアミド（ＤＭＦ）中で撹拌後、そこに１３ｍｇのテトラキス（４－カルボキシフェニル）ポルフィリンと１４ｍＬの蟻酸を加えた。その溶液を密閉容器内で４０３Ｋの温度で熱処理することで粉末を得た。その粉末を洗浄し、乾燥させることで比較例３の試料を得た。
(Comparative Example 3)
An organic metal structure (PCN-222) using a Zr compound having iron-free porphyrin as a ligand was synthesized by the method shown below.
After stirring 75 mg of ZrOCl 2.8H 2 O in 20 mL of dimethylformamide (DMF), 13 mg of tetrakis (4-carboxyphenyl) porphyrin and 14 mL of formic acid were added thereto. The solution was heat treated in a closed container at a temperature of 403 K to obtain a powder. The powder was washed and dried to obtain a sample of Comparative Example 3.
その試料の活性を実施例１の活性評価法と同様の方法で評価した。
その結果、図６に示すように、アセトンの４時間後の生成量は２００ｐｐｍ程度であり、実施例１，３に比べて十分低く、活性は高くなかった。
The activity of the sample was evaluated by the same method as the activity evaluation method of Example 1.
As a result, as shown in FIG. 6, the amount of acetone produced after 4 hours was about 200 ppm, which was sufficiently lower than that of Examples 1 and 3, and the activity was not high.
本発明の光触媒は、可視光から赤外光に渡る幅広く、かつ室内、室外ともに溢れている光によって、高い効率で、しかも耐久力を持って有機物を二酸化炭素に至る炭素含有物質まで酸化分解するものである。そして、本発明の光触媒は、粉末状に限らず、各種素材面に薄膜として被着させることも可能である。したがって、本発明により、有害な有機物を、可視光を中心とした光で利便性よく害の少ない二酸化炭素などに効率的に分解できるので、民生および産業分野で大いに利用される可能性がある。 The photocatalyst of the present invention decomposes organic substances into carbon-containing substances up to carbon dioxide with high efficiency and durability by a wide range of light from visible light to infrared light, which overflows both indoors and outdoors. It is a thing. The photocatalyst of the present invention is not limited to powder, and can be adhered to various material surfaces as a thin film. Therefore, according to the present invention, harmful organic substances can be efficiently decomposed into carbon dioxide and the like, which are convenient and less harmful with light centered on visible light, and may be widely used in the consumer and industrial fields.
Claims (10)
前記金属化合物クラスターは無機２次元構造単位としてＺｒ金属化合物を含み、
前記金属ポルフィリンは前記金属化合物クラスターの架橋配位子になっており、
前記金属ポルフィリンの金属は、Ｆｅ３＋，Ｆｅ２＋の少なくとも何れか１以上である、光触媒。 A metal-organic framework containing metal compound clusters and metal porphyrins.
The metal compound cluster contains a Zr metal compound as an inorganic two-dimensional structural unit and contains.
The metal porphyrin serves as a cross-linking ligand for the metal compound cluster, and is used as a cross-linking ligand.
A photocatalyst in which the metal of the metal porphyrin is at least one of Fe 3+ and Fe 2+ .
前記金属化合物クラスターは無機２次元構造単位としてＺｒ金属化合物を含み、
前記金属ポルフィリン誘導体は前記金属化合物クラスターの架橋配位子になっており、
前記金属ポルフィリン誘導体の金属は、Ｆｅ３＋，Ｆｅ２＋の少なくとも何れか１以上である、光触媒。 A metal-organic framework containing a metal compound cluster and a metal porphyrin derivative.
The metal compound cluster contains a Zr metal compound as an inorganic two-dimensional structural unit and contains.
The metal porphyrin derivative serves as a cross-linking ligand for the metal compound cluster.
A photocatalyst in which the metal of the metal porphyrin derivative is at least one of Fe 3+ and Fe 2+ .
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