JP7072797B2 - Auxiliary catalyst for compounds and photocatalysts - Google Patents
Auxiliary catalyst for compounds and photocatalysts Download PDFInfo
- Publication number
- JP7072797B2 JP7072797B2 JP2018027663A JP2018027663A JP7072797B2 JP 7072797 B2 JP7072797 B2 JP 7072797B2 JP 2018027663 A JP2018027663 A JP 2018027663A JP 2018027663 A JP2018027663 A JP 2018027663A JP 7072797 B2 JP7072797 B2 JP 7072797B2
- Authority
- JP
- Japan
- Prior art keywords
- photocatalyst
- formula
- catalyst
- present
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 150000001875 compounds Chemical class 0.000 title claims description 64
- 239000011941 photocatalyst Substances 0.000 title claims description 57
- 239000003054 catalyst Substances 0.000 title description 14
- 239000003426 co-catalyst Substances 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 22
- 230000001699 photocatalysis Effects 0.000 claims description 13
- 230000001678 irradiating effect Effects 0.000 claims description 5
- 230000000694 effects Effects 0.000 description 25
- 239000001257 hydrogen Substances 0.000 description 19
- 229910052739 hydrogen Inorganic materials 0.000 description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 15
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 12
- 229910000510 noble metal Inorganic materials 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- 238000000354 decomposition reaction Methods 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 229910052725 zinc Inorganic materials 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 150000001721 carbon Chemical group 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229910052793 cadmium Inorganic materials 0.000 description 5
- 150000004696 coordination complex Chemical class 0.000 description 5
- 238000004949 mass spectrometry Methods 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000002041 carbon nanotube Substances 0.000 description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- WTHJTVKLMSJXEV-UHFFFAOYSA-N 2-(4-aminopyridin-2-yl)pyridin-4-amine Chemical group NC1=CC=NC(C=2N=CC=C(N)C=2)=C1 WTHJTVKLMSJXEV-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- CMNUYDSETOTBDE-UHFFFAOYSA-N 1-benzyl-4h-pyridine-3-carboxamide Chemical compound C1=CCC(C(=O)N)=CN1CC1=CC=CC=C1 CMNUYDSETOTBDE-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- -1 WO 3 Inorganic materials 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 229910003472 fullerene Inorganic materials 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 239000008204 material by function Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012982 x-ray structure analysis Methods 0.000 description 2
- OMMPOLDESJSYDZ-UHFFFAOYSA-N 2-pyridin-2-ylpyridine-3,4-diamine Chemical group NC1=CC=NC(C=2N=CC=CC=2)=C1N OMMPOLDESJSYDZ-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- HXEACLLIILLPRG-YFKPBYRVSA-N L-pipecolic acid Chemical compound [O-]C(=O)[C@@H]1CCCC[NH2+]1 HXEACLLIILLPRG-YFKPBYRVSA-N 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 229910019899 RuO Inorganic materials 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- 229910003071 TaON Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 239000000412 dendrimer Substances 0.000 description 1
- 229920000736 dendritic polymer Polymers 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000012992 electron transfer agent Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- HXEACLLIILLPRG-RXMQYKEDSA-N l-pipecolic acid Natural products OC(=O)[C@H]1CCCCN1 HXEACLLIILLPRG-RXMQYKEDSA-N 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N nickel(II) oxide Inorganic materials [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 230000002165 photosensitisation Effects 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- DJXYWDRBAAVVSG-UHFFFAOYSA-J potassium;tetrachloroplatinum Chemical compound [K].Cl[Pt](Cl)(Cl)Cl DJXYWDRBAAVVSG-UHFFFAOYSA-J 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
Landscapes
- Pyridine Compounds (AREA)
- Catalysts (AREA)
Description
特許法第３０条第２項適用 （１）平成２９年１１月１１日に「第２回光触媒国際シンポジウム／第２３回日中機能材料学会合同シンポジウム（Ｐｈｏｔｏｃａｔａｌｙｓｉｓ ２ ＆ ＳＩＥＭＭＥ’２３）」のウェブサイトにて公開 （２）平成２９年１２月１日に「東京理科大学総合研究院光触媒国際研究センター（Ｐｈｏｔｏｃａｔａｌｙｓｉｓ Ｉｎｔｅｒｎａｔｉｏｎａｌ Ｒｅｓｅａｒｃｈ Ｃｅｎｔｅｒ（ＰＩＲＣ））」が発行した「Ｐｈｏｔｏｃａｔａｌｙｓｉｓ ２ ＆ ＳＩＥＭＭＥ’２３」にて発表 （３）平成２９年１２月２日に「第２回光触媒国際シンポジウム／第２３回日中機能材料学会合同シンポジウム（Ｐｈｏｔｏｃａｔａｌｙｓｉｓ ２ ＆ ＳＩＥＭＭＥ’２３）」のポスター発表にて発表Application of
本発明は、光触媒用助触媒作用を有する新規な化合物、前記化合物を含む光触媒用助触媒、及び前記光触媒用助触媒を用いる水の分解方法に関する。 The present invention relates to a novel compound having a photocatalytic cocatalytic action, a photocatalytic cocatalyst containing the compound, and a method for decomposing water using the photocatalytic cocatalyst.
近年、省エネルギーの観点から太陽エネルギーの利用が盛んに検討されており、太陽エネルギーを利用する形態の一つとして、光触媒を使用して太陽エネルギーを実際に利用可能なエネルギーへ変換することが検討されている。例えば、光触媒を用いることにより、太陽エネルギーを利用して水を分解して水素と酸素を製造する技術が検討されている。しかし、光触媒だけでは、その効果はあまり高くないため、触媒効果を向上させるための助触媒が必要となる。このような助触媒としては様々なものが提案されているが（特許文献１、特許文献２）、実際に使用できる程度の効果を有するのは、白金等の貴金属を使用した助触媒であった。しかし、白金等の貴金属は、高価であり、資源的にも存在量が限られている。そのため、他の金属を用いた助触媒の開発が求められていたが、光触媒の活性を満足できる程度に向上させることのできる助触媒は得られていなかった。
In recent years, the use of solar energy has been actively studied from the viewpoint of energy saving, and as one of the forms of using solar energy, it has been studied to convert solar energy into actually usable energy by using a photocatalyst. ing. For example, a technique for producing hydrogen and oxygen by decomposing water by using solar energy by using a photocatalyst is being studied. However, the effect of the photocatalyst alone is not so high, so an auxiliary catalyst for improving the catalytic effect is required. Although various such co-catalysts have been proposed (
本発明は、上記問題点を解決し、貴金属を使用しなくても光触媒に対する優れた活性向上効果を有する助触媒を提供することを課題とする。 An object of the present invention is to solve the above problems and to provide a co-catalyst having an excellent effect of improving activity on a photocatalyst without using a noble metal.
本発明者らは、金属錯体系の助触媒としては、Ｐｔ、Ｒｕなどを中心とする貴金属系錯体が有効であることが定説であるところ、貴金属を使用しない助触媒の開発を目指して検討を開始した。鋭意検討を重ねたところ、これまで検討されていなかったビピリジン配位子に対してアミン基を修飾したＣｕ、Ｎｉ等の遷移金属錯体を新規に合成したところ、助触媒としての効果が非常に高く、特にＰｔ等の貴金属錯体と組み合わせて使用すると、貴金属錯体単独で使用する場合に比べて４０％の性能向上を示すことを見いだした。これまでも、貴金属以外の金属を用いた錯体系触媒は、いくつか提案されているが、本発明者らが見いだしたような単純な配位子構造を有する錯体で効果を示した事例はみられなかった。本発明はこのようにして完成されたものである。 The present inventors have established that a noble metal-based complex centered on Pt, Ru, etc. is effective as a metal complex-based co-catalyst. It started. After repeated diligent studies, a new transition metal complex such as Cu, Ni, etc., in which an amine group was modified for a bipyridine ligand, which had not been studied so far, was newly synthesized, and the effect as a co-catalyst was very high. In particular, it has been found that when used in combination with a noble metal complex such as Pt, the performance is improved by 40% as compared with the case where the noble metal complex is used alone. Although several complex catalysts using metals other than precious metals have been proposed so far, there are cases where a complex having a simple ligand structure as found by the present inventors was effective. I couldn't. The present invention has been completed in this way.
すなわち、本発明は以下に示す事項により特定されるものである。
［１］式（１）又は（２）で表される化合物。
［２］式（１）で表される化合物が、式（１-１）で表される化合物である上記［１］記載の化合物。
［５］光触媒と、光触媒用助触媒又は電子メディエータの存在下、光を照射して水の分解を行う方法であって、前記光触媒用助触媒又は電子メディエータとして上記［４］記載の光触媒用助触媒又は電子メディエータを用いることを特徴とする水の分解方法。
That is, the present invention is specified by the following matters.
[1] A compound represented by the formula (1) or (2).
[2] The compound according to the above [1], wherein the compound represented by the formula (1) is a compound represented by the formula (1-1).
[5] A method of irradiating light to decompose water in the presence of a photocatalyst and a photocatalyst auxiliary catalyst or an electronic mediator, wherein the photocatalyst auxiliary catalyst or the electronic mediator is the photocatalyst auxiliary according to the above [4]. A method for decomposing water, which comprises using a catalyst or an electronic mediator.
本発明の化合物は、光触媒に対する助触媒として使用すると優れた活性向上効果を有する。特に光触媒による水の分解において、優れた活性向上効果を示し、Ｐｔ錯体等の貴金属系助触媒と共に使用すると、水素の発生反応に対する優れた活性向上効果を示し、水素の生成量を増加させることができる。そのため、貴金属助触媒の使用量を減らすことができるので、コスト削減と資源維持の観点からの貴金属の使用量の低減を行うことができる。また、本発明の化合物は、単純な配位子構造を有するので、合成が容易である。 The compound of the present invention has an excellent activity improving effect when used as a co-catalyst for a photocatalyst. Especially in the decomposition of water by a photocatalyst, it shows an excellent activity improving effect, and when used together with a noble metal-based co-catalyst such as a Pt complex, it shows an excellent activity improving effect on a hydrogen generation reaction and can increase the amount of hydrogen produced. can. Therefore, since the amount of the noble metal co-catalyst used can be reduced, the amount of the noble metal used can be reduced from the viewpoint of cost reduction and resource maintenance. Moreover, since the compound of the present invention has a simple ligand structure, it is easy to synthesize.
本発明の化合物は、以下の式（１）又は（２）で表される化合物である。 The compound of the present invention is a compound represented by the following formula (1) or (2).
式（１）におけるＭ１は、Ｃｕ、Ｚｎ又はＣｄを表す。その中でも、活性向上効果をより高める観点、金属がより安価である観点からＣｕが好ましい。また、式（２）におけるＭ２は、Ｎｉ、Ｍｎ又はＺｎを表す。その中でも、活性向上効果をより高める観点、金属の仕事関数が高く電子の捕集能力がより高いという観点からＮｉが好ましい。式（１）及び式（２）におけるＸは各ピリジン環の他のピリジン環と縮合していない炭素原子上に置換しており、式（１）におけるｋ、ｌ、ｍ及びｎは炭素原子上に置換しているＸの個数を表す。例えば、（Ｘ）ｋにおいてｋ＝１とは、当該ピリジン環の１個の炭素原子上にＸが１個置換している状態を表し、ｋ＝２とは、当該ピリジン環の２個の炭素原子上に、それぞれＸが１個ずつ置換している状態を表し、ｋ＝３とは、当該ピリジン環の３個の炭素原子上に、それぞれＸが１個ずつ置換している状態を表す。また、式（２）におけるａ、ｂ、ｃ、ｄ、ｅ及びｆも同様である。また、本発明の化合物は、光触媒に対する助触媒作用、あるいは電子メディエータ作用を有するものであるが、その作用を阻害しない限り各ピリジン環にＸ以外の置換基を有していてもよい。 M1 in the formula (1) represents Cu, Zn or Cd. Among them, Cu is preferable from the viewpoint of further enhancing the activity improving effect and from the viewpoint of cheaper metal. Further, M2 in the formula (2) represents Ni, Mn or Zn. Among them, Ni is preferable from the viewpoint of further enhancing the activity improving effect and from the viewpoint of having a high work function of the metal and a higher electron collecting ability. X in the formula (1) and the formula (2) is substituted on the carbon atom which is not condensed with the other pyridine ring of each pyridine ring, and k, l, m and n in the formula (1) are on the carbon atom. Represents the number of Xs replaced with. For example, in (X) k , k = 1 represents a state in which one X is substituted on one carbon atom of the pyridine ring, and k = 2 means two carbon atoms of the pyridine ring. A state in which one X is substituted on each atom is represented, and k = 3 represents a state in which one X is substituted on each of the three carbon atoms of the pyridine ring. The same applies to a, b, c, d, e and f in the formula (2). Further, the compound of the present invention has a cocatalytic action or an electron mediator action on a photocatalyst, but each pyridine ring may have a substituent other than X as long as the action is not inhibited.
式（１）及び式（２）のＸにおけるＣ１～Ｃ６のアルキル基とは、置換基を有してもよい炭素数１～６の直鎖状又は分岐状のアルキル基である。例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ｎ－ペンチル基、イソペンチル基、ネオペンチル基、ｎ－へキシル基等が挙げられる。また、上記「置換基を有していてもよい」の置換基としては、ハロゲン原子、アルコキシ基、アリール基等が挙げられる。 The alkyl groups C1 to C6 in X of the formulas (1) and (2) are linear or branched alkyl groups having 1 to 6 carbon atoms which may have a substituent. For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group. And so on. Further, examples of the above-mentioned "may have a substituent" substituent include a halogen atom, an alkoxy group, an aryl group and the like.
式（１）及び式（２）における１～３個のＸは、各ピリジン環において、他のピリジン環と縮合している炭素原子を除く４個の炭素原子のいずれの炭素原子上に置換していてもよい。Ｘの個数は１～２個が好ましく、１個がより好ましい。また、少なくとも１個のＸが、ピリジン環の窒素原子に対してｐ位にある炭素原子上に置換していることが好ましい。ＸはＮＲ１Ｒ２で表され、Ｒ１及びＲ２は、それぞれ水素又はＣ１～Ｃ６のアルキル基を表し、Ｒ１とＲ２は同じでも異なっていてもよい。Ｒ１及びＲ２の少なくとも一方は水素であることが好ましく、両方が水素であることがより好ましい。Ｘは同じでも異なっていてもよく、例えば、一つのピリジン環が複数のＸを有する場合、それぞれのＸは同じでも異なっていてもよい。また、異なるピリジン環が有するＸ同士は同じでも異なっていてもよい。ＸはＮＨ２であり、全てのピリジン環において窒素原子に対してｐ位にある炭素原子上に置換していることが好ましい。 The 1 to 3 Xs in the formulas (1) and (2) are substituted on any carbon atom of the four carbon atoms except the carbon atom condensed with the other pyridine ring in each pyridine ring. May be. The number of X is preferably 1 to 2, and more preferably 1. Further, it is preferable that at least one X is substituted on the carbon atom at the p-position with respect to the nitrogen atom of the pyridine ring. X is represented by NR 1 R 2 , R 1 and R 2 represent hydrogen or an alkyl group of C1 to C6, respectively, and R 1 and R 2 may be the same or different. At least one of R 1 and R 2 is preferably hydrogen, and more preferably both are hydrogen. The Xs may be the same or different, for example, if one pyridine ring has a plurality of Xs, each X may be the same or different. Further, the Xs of different pyridine rings may be the same or different. X is NH 2 , and it is preferable that all pyridine rings are substituted on the carbon atom at the p-position with respect to the nitrogen atom.
式（１）で表される化合物としては、具体的には、以下に示す化合物（１－１）を例示することができる。 Specifically, as the compound represented by the formula (1), the compound (1-1) shown below can be exemplified.
また、式（２）で表される化合物としては、具体的には、以下に示す化合物（２－１）を例示することができる。 Further, as the compound represented by the formula (2), specifically, the compound (2-1) shown below can be exemplified.
（化合物の合成）
本発明の式（１）及び式（２）で表される化合物の合成法は、特に制限されるものではないが、例えば以下の方法を挙げることができる。式（１）で表される化合物を合成する場合は、Ｃｕ、Ｚｎ又はＣｄの塩化物を、式（２）で表される化合物を合成する場合は、Ｎｉ、Ｍｎ又はＺｎの塩化物をエタノール等の溶媒に溶解した溶液（溶液Ａ）を準備する。また、４，４’－ジアミノ－２，２’－ビピリジル等のジアミノビピリジルを溶解した溶液（溶液Ｂ）を準備する。溶液Ａを溶液Ｂに添加して撹拌した後、ジエチルエーテル等の有機溶媒を添加して静置する。静置後、析出物を分離することにより本発明の化合物を得ることができる。静置は、０～５℃で行うことが好ましく、静置時間としては、１２～２４時間が好ましい。
(Compound synthesis)
The method for synthesizing the compounds represented by the formulas (1) and (2) of the present invention is not particularly limited, and examples thereof include the following methods. When synthesizing the compound represented by the formula (1), the chloride of Cu, Zn or Cd is used, and when synthesizing the compound represented by the formula (2), the chloride of Ni, Mn or Zn is used as ethanol. A solution (solution A) dissolved in a solvent such as is prepared. Further, a solution (solution B) in which diaminobipyridyl such as 4,4'-diamino-2,2'-bipyridyl is dissolved is prepared. After the solution A is added to the solution B and stirred, an organic solvent such as diethyl ether is added and the mixture is allowed to stand. After standing, the compound of the present invention can be obtained by separating the precipitate. The standing time is preferably 0 to 5 ° C., and the standing time is preferably 12 to 24 hours.
（光触媒用助触媒、電子メディエータ）
本発明の式（１）又は式（２）で表される化合物は、光触媒用助触媒として用いることができる。助触媒とは、主の触媒成分が単独で示す触媒作用を強化する作用を有する補助成分のことであり、光触媒用助触媒とは、主の触媒成分である光触媒に対して、前記作用を有する補助成分のことをいう。本発明の光触媒用助触媒は、本発明の式（１）又は式（２）で表される化合物のみからなっていてもよく、助触媒作用を阻害しない限り、あるいは助触媒作用を更に向上させる目的で、他の成分を含んでいてもよい。本発明の光触媒用助触媒が用いられる光触媒は、特に制限されるものではないが、例えば、ＴｉＯ２、ＷＯ３、ＳｒＴｉＯ３、ＣａＴｉＯ３、Ｌａ２Ｔｉ２Ｏ７、Ｔａ２Ｏ５、ＺｒＯ２、ＢｉＶＯ４、ＡｇＮｂＯ３、ＡｇＰｂＴｉ２Ｏ６、ＲｂＰｂ２Ｎｂ３Ｏ１０、Ｉｎ２Ｏ３－（ＺｎＯ）３、ＩｎＴａＯ４、Ｂｉ２ＭｏＯ６、Ｂｉ２ＷＯ６、ＢｉＹＷＯ６、Ａｇ３ＶＯ４、Ｉｎ２－ｘＺｎｘＣｕ２Ｏ５、ＡＢｉＯ２（ＡはＮａ、Ｋ、Ｌｉ、Ａｇ等の一価金属）、ＴａＯＮ、Ｓｍ２Ｔｉ２Ｓ２Ｏ５、ＢａＮｂＯ２Ｎ、ＳｒＴａＯ２Ｎ、ＬａＴａＯＮ２、Ｓｒ２ＯＮ２、ＮａＴｉＯＳ２、ＺｒＯＳ、カーボンナノチューブ系光触媒等を挙げることができ、これらは単独で用いてもよく、２種以上を混合して用いてもよい。カーボンナノチューブ系光触媒としては、例えば、カーボンナノチューブ(シグマ-アルドリッチ製)とデンドリマーを修飾したフラーレン(フラロデンドロン)からなる複合体型光触媒等を挙げることができる。本発明の式（１）又は式（２）で表される化合物は、水溶性を示すとともに、多くの有機溶媒にも可溶なため、次に示す水の分解反応だけでなく、選択的有機合成等の幅広い光触媒反応において適用可能である。また、本発明の式（１）又は式（２）で表される化合物は、各種反応において電子の伝達を行う電子伝達剤である電子メディエータとして用いることができる。
(Auxiliary catalyst for photocatalyst, electronic mediator)
The compound represented by the formula (1) or the formula (2) of the present invention can be used as a co-catalyst for a photocatalyst. The co-catalyst is an auxiliary component having an action of enhancing the catalytic action exhibited by the main catalyst component alone, and the photocatalytic co-catalyst has the above-mentioned action on the photocatalyst which is the main catalytic component. Auxiliary ingredient. The cocatalyst for a photocatalyst of the present invention may consist only of the compound represented by the formula (1) or the formula (2) of the present invention, as long as the cocatalytic action is not inhibited or the cocatalytic action is further improved. For the purpose, it may contain other components. The photocatalyst to which the cocatalyst for the photocatalyst of the present invention is used is not particularly limited, and is, for example, TiO 2 , WO 3 , SrTiO 3 , CaTIO 3 , La 2 Ti 2 O 7 , Ta 2 O 5 , ZrO 2 . , BiVO 4 , AgNbO 3 , AgPbTi 2 O 6 , RbPb 2 Nb 3 O 10 , In 2 O 3- (ZnO) 3 , InTaO 4 , Bi 2 MoO 6 , Bi 2 O 4, BiYWO 6 , Ag In 2-x Zn x Cu 2 O 5 , ABiO 2 (A is a monovalent metal such as Na, K, Li, Ag), TaON, Sm 2 Ti 2 S 2 O 5 , BaNbO 2 N, SrTaO 2 N, LaTaON 2 , Sr 2 ON 2 , NaTiOS 2 , ZrOS, carbon nanotube-based photocatalyst and the like can be mentioned, and these may be used alone or in combination of two or more. Examples of the carbon nanotube-based photocatalyst include a composite photocatalyst composed of carbon nanotubes (manufactured by Sigma-Aldrich) and fullerene (fullerene drone) modified with a dendrimer. Since the compound represented by the formula (1) or the formula (2) of the present invention is water-soluble and soluble in many organic solvents, it is not only the following water decomposition reaction but also selective organic. It can be applied to a wide range of photocatalytic reactions such as synthesis. Further, the compound represented by the formula (1) or the formula (2) of the present invention can be used as an electron mediator which is an electron transfer agent that transfers electrons in various reactions.
（水の分解方法）
本発明の光触媒用助触媒は、光触媒を用いた水の分解における助触媒として用いることがでる。本発明の水の分解方法は、光触媒及び光触媒用助触媒の存在下、光を照射して水の分解を行う方法であって、前記光触媒用助触媒として本発明の光触媒用助触媒を用いることを特徴とする。本発明の水の分解方法に用いる光触媒は、特に制限されず、水の分解に通常用いられる光触媒を用いることができ、例えば、上記（光触媒用助触媒）の段落で例示した光触媒を用いることができる。また、本発明の水の分解方法では、水と光触媒及び光触媒用助触媒を接触させる方法、光触媒と光触媒用助触媒を混合する、光触媒に光触媒用助触媒を担持させる等の光触媒と光触媒用助触媒を組み合わせる方法、光の照射方法、反応時の温度、使用する装置などは従来公知のものを適用することができる。本発明の水の分解方法では、本発明の光触媒用助触媒を他の助触媒と組み合わせて用いることができる。他の助触媒としては、特に制限されるものではないが、例えば、Ｐｔ、Ｐｄ、Ｒｈ、Ｒｕ、Ｎｉ、Ａｕ、Ｆｅ、ＮｉＯ、ＲｕＯ２、ＩｒＯ２、Ｒｈ２Ｏ３、Ｃｒ－Ｒｈ複合酸化物、コアシェル型Ｒｈ／Ｃｒ２Ｏ３、Ｐｔ／Ｃｒ２Ｏ３、Ｈ２ＰｔＣｌ４、Ｋ２ＰｔＣｌ６、Ｋ２ＰｔＣｌ４等の白金錯体などの還元反応助触媒、Ｍｇ、Ｔｉ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｇａ、Ｒｕ、Ｒｈ、Ｐｄ、Ａｇ、Ｃｄ、Ｉｎ、Ｃｅ、Ｔａ、Ｗ、Ｉｒ、Ｐｔ、Ｐｂ等の金属、又はこれらの酸化物若しくは複合酸化物などの酸化反応助触媒を挙げることができる。また、本発明の水の分解方法では、犠牲剤を用いることができる。犠牲剤とは、光触媒による反応過程で、自らは変質しつつ反応を進行させる化合物のことであり、犠牲剤としては、特に制限されるものではなく公知の犠牲剤を使用することができる。例えば、還元剤として働くものとしては、トリエタノールアミン、アスコルビン酸、１－ベンジル－１，４－ジヒドロニコチンアミド等を挙げることができ、酸化剤として働くものとしては、セリウム（ＩＶ）イオン、銀イオン等を挙げることができる。本発明の水の分解方法は、例えば、水に光触媒、本発明の光触媒用助触媒、必要に応じて他の助触媒、犠牲剤、ｐＨ調整剤等を添加して、可視光又は紫外線等の光を照射することにより行うことができる。例えば、水に光触媒及び本発明の光触媒用助触媒、必要に応じて他の光触媒用助触媒を添加して、撹拌しながら光を照射してもよく、光触媒に本発明の光触媒用助触媒を担持させて水に添加してもよく、必要に応じてさらに他の光触媒用助触媒を担持させてもよい。
(How to decompose water)
The cocatalyst for a photocatalyst of the present invention can be used as a cocatalyst in the decomposition of water using a photocatalyst. The method for decomposing water of the present invention is a method of irradiating light to decompose water in the presence of a photocatalyst and a photocatalyst cocatalyst, and the photocatalyst cocatalyst of the present invention is used as the photocatalyst cocatalyst. It is characterized by. The photocatalyst used in the water decomposition method of the present invention is not particularly limited, and a photocatalyst usually used for water decomposition can be used. For example, the photocatalyst exemplified in the above paragraph (auxiliary catalyst for photocatalyst) may be used. can. Further, in the method for decomposing water of the present invention, a method of contacting water with a photocatalyst and a photocatalyst auxiliary catalyst, a method of mixing a photocatalyst and a photocatalyst auxiliary catalyst, a photocatalyst supporting a photocatalyst auxiliary catalyst, etc. Conventionally known methods such as a method for combining catalysts, a method for irradiating light, a temperature at the time of reaction, and an apparatus to be used can be applied. In the water decomposition method of the present invention, the photocatalytic co-catalyst of the present invention can be used in combination with other co-catalysts. Other co-catalysts are not particularly limited, but are, for example, Pt, Pd, Rh, Ru, Ni, Au, Fe, NiO, RuO 2 , IrO 2 , Rh 2 O 3 , and Cr—Rh composite oxidation. Platinum complexes such as core-shell type Rh / Cr 2 O 3 , Pt / Cr 2 O 3 , H 2 PtCl 4 , K 2 PtCl 6 , K 2 PtCl 4 , etc. , Co, Ni, Cu, Ga, Ru, Rh, Pd, Ag, Cd, In, Ce, Ta, W, Ir, Pt, Pb and other metals, or oxides or composite oxides thereof. A catalyst can be mentioned. Further, in the method for decomposing water of the present invention, a sacrificial agent can be used. The sacrificial agent is a compound that advances the reaction while being altered by itself in the reaction process by the photocatalyst, and the sacrificial agent is not particularly limited, and a known sacrificial agent can be used. For example, those that act as a reducing agent include triethanolamine, ascorbic acid, 1-benzyl-1,4-dihydronicotinamide, and the like, and those that act as an oxidizing agent include cerium (IV) ion and silver. Ions and the like can be mentioned. The method for decomposing water of the present invention is, for example, adding a photocatalyst, a cocatalyst for a photocatalyst of the present invention, another cocatalyst, a sacrificial agent, a pH adjuster, etc. to water, and using visible light or ultraviolet rays. It can be done by irradiating with light. For example, a photocatalyst, a photocatalyst cocatalyst of the present invention, and another photocatalyst cocatalyst may be added to water and irradiated with light while stirring, and the photocatalyst cocatalyst of the present invention may be added to the photocatalyst. It may be carried and added to water, and if necessary, another cocatalyst for a photocatalyst may be carried.
本発明の水の分解方法では、カーボンナノチューブ系光触媒等の光触媒と、助触媒として、貴金属錯体等の還元反応助触媒と本発明の光触媒用助触媒を用いることにより、水の分解による水素発生反応を行うことができる。この際、トリエタノールアミン、１－ベンジル－１，４－ジヒドロニコチンアミド等の還元剤として働く犠牲剤を使用することが好ましい。また、貴金属錯体の還元反応助触媒としては、白金（Ｐｔ）錯体が好ましい。Ｐｔ錯体としては、例えば、Ｈ２ＰｔＣｌ４、Ｋ２ＰｔＣｌ６、Ｋ２ＰｔＣｌ４等を挙げることができる。本発明の水の分解方法によれば、貴金属系助触媒の使用量を減らすことができ、また、貴金属系助触媒を単独で使用した場合を上回る水素発生効率を得ることができる。 In the water decomposition method of the present invention, a photocatalyst such as a carbon nanotube-based photocatalyst, a reduction reaction co-catalyst such as a noble metal complex, and a photocatalyst co-catalyst of the present invention are used as co-catalysts to generate a hydrogen generation reaction by decomposing water. It can be performed. At this time, it is preferable to use a sacrificial agent that acts as a reducing agent, such as triethanolamine and 1-benzyl-1,4-dihydronicotinamide. Further, as the reduction reaction co-catalyst of the noble metal complex, a platinum (Pt) complex is preferable. Examples of the Pt complex include H 2 PtCl 4 , K 2 PtCl 6 , K 2 PtCl 4 , and the like. According to the water decomposition method of the present invention, the amount of the noble metal-based co-catalyst used can be reduced, and hydrogen generation efficiency higher than that when the noble metal-based co-catalyst is used alone can be obtained.
以下に、実施例において本発明をより詳細に説明するが、本発明の技術範囲は、これらに限定されるものではない。 Hereinafter, the present invention will be described in more detail in Examples, but the technical scope of the present invention is not limited thereto.
［実施例１］
（式（１－１）で表される化合物の合成）
塩化銅（II）０．０４ｇをエタノール１ｍＬに溶解した（溶液Ａとする）。次に、４，４’－ジアミノ－２，２’－ビピリジル０．１３０ｇをエタノール１０ｍｌで溶解した（溶液Ｂとする）。溶液Ａを溶液Ｂに添加して密閉後、室温で５時間撹拌した。その後ジエチルエーテル１０ｍＬを添加し、冷蔵庫中５℃で２４時間程度静置して析出物を得た。吸引ろ過し、ジエチルエーテルで２回洗浄後、乾燥して化合物を得た。得られた化合物の構造を、単結晶Ｘ線構造解析（測定装置：ＡＰＥＸ II Ｕｌｔｒａ、Ｂｒｕｋｅｒ社製）及び質量分析（測定装置：Ｄａｌｔｏｎｉｃｓ、Ｂｒｕｋｅｒ社製）により同定したところ、式（１－１）に示す構造の錯体であった。
[Example 1]
(Synthesis of compound represented by formula (1-1))
0.04 g of copper (II) chloride was dissolved in 1 mL of ethanol (referred to as solution A). Next, 0.130 g of 4,4'-diamino-2,2'-bipyridyl was dissolved in 10 ml of ethanol (referred to as solution B). Solution A was added to solution B, sealed, and then stirred at room temperature for 5 hours. Then, 10 mL of diethyl ether was added, and the mixture was allowed to stand in a refrigerator at 5 ° C. for about 24 hours to obtain a precipitate. It was suction filtered, washed twice with diethyl ether, and dried to obtain a compound. The structure of the obtained compound was identified by single crystal X-ray structure analysis (measuring device: APEX II Ultra, manufactured by Bruker) and mass spectrometry (measuring device: Daltonics, manufactured by Bruker). It was a complex having the structure shown in.
（助触媒効果試験）
光触媒活性をより簡便に評価するため、可視光領域に光増感作用を示すエリシロシンＢを用いて、本発明の化合物の助触媒効果を検証した。水１００ｍＬに、１１３．６４μＭのエリシロシンＢ、犠牲剤として１５ｍＬのトリエタノールアミンを加え、本発明の式（１－１）で表される化合物を濃度を変えて添加した。これに、５００ＷＸｅランプを用いて可視光（λ≧４２０ｎｍ）を照射して水素発生量を測定した。水素発生量はガスクロマトグラフ(島津製作所製 ＧＣ－８Ａ、分析カラム：ＭＳ－５Ａ)を用いて定量した。本発明の式（１－１）で表される化合物の添加量は、エリシロシンＢの濃度に対して２０％、２２％、２３％、２６％、３０％とした。結果を図１に示す。図１に示された線の上から、２３％、２２％、２６％、３０％、２０％である。いずれの場合においても助触媒効果がみられ、２３％の場合が最も助触媒効果が高かった。
(Co-catalyst effect test)
In order to evaluate the photocatalytic activity more easily, the cocatalytic effect of the compound of the present invention was verified using erythirocin B, which exhibits a photosensitizing effect in the visible light region. To 100 mL of water, 113.64 μM erythirocin B and 15 mL of triethanolamine as a sacrificial agent were added, and the compound represented by the formula (1-1) of the present invention was added at different concentrations. This was irradiated with visible light (λ ≧ 420 nm) using a 500 WXe lamp, and the amount of hydrogen generated was measured. The amount of hydrogen generated was quantified using a gas chromatograph (GC-8A manufactured by Shimadzu Corporation, analytical column: MS-5A). The amount of the compound represented by the formula (1-1) of the present invention was 20%, 22%, 23%, 26%, and 30% with respect to the concentration of erythirosin B. The results are shown in FIG. From the top of the line shown in FIG. 1, 23%, 22%, 26%, 30%, 20%. The co-catalyst effect was observed in all cases, and the co-catalyst effect was the highest in the case of 23%.
［実施例２］
（式（２－１）で表される化合物の合成）
塩化ニッケル（II）０．０４ｇをエタノール１ｍＬに溶解した（溶液Ａとする）。次に、４，４’－ジアミノ－２，２’－ビピリジル０．１０１ｇをエタノール１０ｍｌで溶解した（溶液Ｂとする）。溶液Ａを溶液Ｂに添加して密閉後、室温で５時間撹拌した。その後ジエチルエーテル１０ｍＬを添加し、冷蔵庫中５℃で２４時間程度静置して析出物を得た。吸引ろ過し、ジエチルエーテルで２回洗浄後、乾燥して化合物を得た。得られた化合物の構造を、実施例１と同様に同定したところ、式（２－１）に示す構造の錯体であった。
[Example 2]
(Synthesis of compound represented by formula (2-1))
0.04 g of nickel (II) chloride was dissolved in 1 mL of ethanol (referred to as solution A). Next, 0.101 g of 4,4'-diamino-2,2'-bipyridyl was dissolved in 10 ml of ethanol (referred to as solution B). Solution A was added to solution B, sealed, and then stirred at room temperature for 5 hours. Then, 10 mL of diethyl ether was added, and the mixture was allowed to stand in a refrigerator at 5 ° C. for about 24 hours to obtain a precipitate. It was suction filtered, washed twice with diethyl ether, and dried to obtain a compound. When the structure of the obtained compound was identified in the same manner as in Example 1, it was a complex having the structure represented by the formula (2-1).
（助触媒効果試験）
水１００ｍＬに、１１３．６４μＭのエリシロシンＢ、犠牲剤として１５ｍＬのトリエタノールアミンを加え、本発明の式（１－１）で表される化合物を２６．３９μＭ加えて、他は実施例１と同様に処理して水素発生量を測定した。また、本発明の式（１－１）で表される化合物を式（２－１）で表される化合物に代えた例でも、水素発生量を測定した。その結果を図２に示す。図２に示されるように、いずれの場合も助触媒効果がみられたが、Ｃｕ錯体を使用した場合の方が効果が高かった。
(Co-catalyst effect test)
To 100 mL of water, 113.64 μM of erythirosin B and 15 mL of triethanolamine as a sacrificial agent were added, and 26.39 μM of the compound represented by the formula (1-1) of the present invention was added, otherwise the same as in Example 1. The amount of hydrogen generated was measured. Further, the amount of hydrogen generated was also measured in an example in which the compound represented by the formula (1-1) of the present invention was replaced with the compound represented by the formula (2-1). The results are shown in FIG. As shown in FIG. 2, the co-catalytic effect was observed in all cases, but the effect was higher when the Cu complex was used.
［実施例３］
水１００ｍＬに、１１３．６４μＭのエリシロシンＢ、犠牲剤として１５ｍＬのトリエタノールアミンを加え、０．４６ｍｇ／ＬのＰｔ（II）錯体（テトラクロロ白金(II)酸カリウム Ｋ２ＰｔＣｌ４）、本発明の式（１－１）で表される化合物を１３．３ｍｇ／Ｌ加えて、他は実施例１と同様に処理して水素発生量を測定した。また、本発明の式（１－１）で表される化合物を式（２－２）で表される化合物に代えた例でも、水素発生量を測定した。その結果を図３に示す。図３の結果から分かるように、本発明の化合物である式（１－１）及び式（２－１）のいずれの化合物もＰｔ（II）錯体を単独で使用した場合に比べ水素の発生量が増加し、活性が向上していることが示された。
[Example 3]
To 100 mL of water, 113.64 μM erythirocin B and 15 mL of triethanolamine as a sacrificial agent were added to add 0.46 mg / L Pt (II) complex (potassium tetrachloroplatinum ( II ) acid K2 PtCl 4 ), the present invention. The compound represented by the formula (1-1) of the above formula (1-1) was added at 13.3 mg / L, and the others were treated in the same manner as in Example 1 to measure the amount of hydrogen generated. Further, the amount of hydrogen generated was also measured in an example in which the compound represented by the formula (1-1) of the present invention was replaced with the compound represented by the formula (2-2). The results are shown in FIG. As can be seen from the results of FIG. 3, both the compounds of the formula (1-1) and the formula (2-1) of the present invention generate hydrogen as compared with the case where the Pt (II) complex is used alone. Was increased, indicating that the activity was improved.
（電気化学的測定）
式（１－１）で表される化合物のサイクリックボルタモグラムを求めた。測定は、式（１－１）で表される化合物濃度をＮ，Ｎ－ジメチルホルムアミド（ＤＭＦ）中１１３．６４Ｍとし、０．１ＭのＮＢｕ４ＰＦ６を支持電解質として用い、参照電極をＡｇ／ＡｇＣｌ、作用電極をグラッシーカーボン、カウンター電極をＰｔワイヤーとした。その結果を図４に示す。図４の結果から分かるように本発明の化合物である式（１－１）で表される化合物は、酸化還元電位が－０．７１Ｖであり、エリシロシンＢから電子を受け取って助触媒作用を発現するのに十分な電位を持っていた。
(Electrochemical measurement)
The cyclic voltammogram of the compound represented by the formula (1-1) was obtained. In the measurement, the compound concentration represented by the formula (1-1) was set to 113.64 M in N, N-dimethylformamide (DMF), 0.1 M NBu 4 PF 6 was used as the supporting electrolyte, and the reference electrode was Ag /. AgCl was used, the working electrode was glassy carbon, and the counter electrode was Pt wire. The results are shown in FIG. As can be seen from the results of FIG. 4, the compound represented by the formula (1-1), which is the compound of the present invention, has a redox potential of −0.71 V, receives an electron from erythirosin B, and exhibits a cocatalytic action. Had enough potential to do.
実施例１と実施例２で調製した化合物のＸ線構造解析により得られた結晶構造パラメータを表１に示す。また、実施例１で調製した化合物の結晶構造図を図５に、実施例２で調製した化合物の結晶構造図を図６に示す。 Table 1 shows the crystal structure parameters obtained by the X-ray structure analysis of the compounds prepared in Examples 1 and 2. Further, FIG. 5 shows a crystal structure diagram of the compound prepared in Example 1, and FIG. 6 shows a crystal structure diagram of the compound prepared in Example 2.
実施例１で調製した化合物の質量分析で得られた質量スペクトルを図７に、実施例２で調製した化合物の質量分析で得られた質量スペクトルを図８に示す。 FIG. 7 shows a mass spectrum obtained by mass spectrometry of the compound prepared in Example 1, and FIG. 8 shows a mass spectrum obtained by mass spectrometry of the compound prepared in Example 2.
本発明の化合物は、光触媒に対する助触媒として使用すると、触媒反応の活性を向上させることができるので、例えば、光触媒を用いた水の分解反応に用いることができ、特に水の分解による水素発生反応に好適に用いることができる。さらに、本発明の化合物は、水だけでなく多くの有機溶媒にも可溶なため、例えば、リシンからのピペコリン酸合成といった選択的有機合成を指向した幅広い光触媒反応においても適用可能である。
When the compound of the present invention is used as a co-catalyst for a photocatalyst, the activity of the catalytic reaction can be improved. Can be suitably used for. Furthermore, since the compound of the present invention is soluble not only in water but also in many organic solvents, it can be applied to a wide range of photocatalytic reactions aimed at selective organic synthesis such as pipecolic acid synthesis from lysine.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018027663A JP7072797B2 (en) | 2018-02-20 | 2018-02-20 | Auxiliary catalyst for compounds and photocatalysts |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018027663A JP7072797B2 (en) | 2018-02-20 | 2018-02-20 | Auxiliary catalyst for compounds and photocatalysts |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2019142800A JP2019142800A (en) | 2019-08-29 |
| JP7072797B2 true JP7072797B2 (en) | 2022-05-23 |
Family
ID=67771847
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2018027663A Active JP7072797B2 (en) | 2018-02-20 | 2018-02-20 | Auxiliary catalyst for compounds and photocatalysts |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP7072797B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7371863B2 (en) * | 2019-12-20 | 2023-10-31 | 本田技研工業株式会社 | Redox medium and hydrogen production method using it |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4045323B2 (en) | 2001-12-28 | 2008-02-13 | アークレイ株式会社 | Colorimetric analysis method and reagent used therefor |
-
2018
- 2018-02-20 JP JP2018027663A patent/JP7072797B2/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4045323B2 (en) | 2001-12-28 | 2008-02-13 | アークレイ株式会社 | Colorimetric analysis method and reagent used therefor |
Non-Patent Citations (11)
| Title |
|---|
| ACTA CRYSTALLOGRAPHICA. SECTION E: STRUCTURE REPORTS ONLINE，2006年，Vol.62, No.8，pp.m1810-1811, supporting information |
| ACTA CRYSTALLOGRAPHICA. SECTION E: STRUCTURE REPORTS ONLINE，2006年，Vol.62, No.9，pp.m2151-m2152, supporting information |
| ACTA CRYSTALLOGRAPHICA. SECTION E: STRUCTURE REPORTS ONLINE，2007年，Vol.63, No.11，pp.m2668, supporting information |
| AUSTRALIAN JOURNAL OF CHEMISTRY，2010年，Vol.63, No.9，pp.1358-1364 |
| Chem.Eur.J.，2005年，Vol.11，pp.5742-5748 |
| Cryst.Growth Des.，2012年，Vol.12，pp.1871-1881 |
| Dalton Transaction，2006年，No.10，pp.1331-1337 |
| Dalton Transaction，2011年，Vol.40，pp5687-5696 |
| Eur.J.Inorg.Chem.，1999年，No.9，pp.1507-1521 |
| Eur.J.Inorg.Chem.，2002年，No.8，pp.1985-1997 |
| Inorganica Chimica Acta，2003年，Vol.343，pp.366-372 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2019142800A (en) | 2019-08-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Saito et al. | Photocatalysis of a dinuclear Ru (II)–Re (I) Complex for CO2 reduction on a solid surface | |
| Benseghir et al. | Co-immobilization of a Rh catalyst and a Keggin polyoxometalate in the UiO-67 Zr-based metal–organic framework: in depth structural characterization and photocatalytic properties for CO2 reduction | |
| Leng et al. | Boosting photocatalytic hydrogen production of porphyrinic MOFs: the metal location in metalloporphyrin matters | |
| Wang et al. | Electronic and steric tuning of catalytic H2 evolution by cobalt complexes with pentadentate polypyridyl-amine ligands | |
| Vennampalli et al. | Electronic effects on a mononuclear Co complex with a pentadentate ligand for catalytic H2 evolution | |
| Li et al. | Simultaneous oxidation of alcohols and hydrogen evolution in a hybrid system under visible light irradiation | |
| Zee et al. | Metal–polypyridyl catalysts for electro-and photochemical reduction of water to hydrogen | |
| JP5724170B2 (en) | Photochemical reaction device | |
| Jiang et al. | Chemical and photocatalytic water oxidation by mononuclear Ru catalysts | |
| WO2012091045A1 (en) | Photochemical reaction device | |
| McKinnon et al. | Synergistic metal–ligand redox cooperativity for electrocatalytic CO2 reduction promoted by a ligand-based redox couple in Mn and Re tricarbonyl complexes | |
| Prevedello et al. | Heterogeneous and homogeneous routes in water oxidation catalysis starting from CuII complexes with tetraaza macrocyclic ligands | |
| Hirahara et al. | New series of dinuclear ruthenium (II) complexes synthesized using photoisomerization for efficient water oxidation catalysis | |
| Walsh et al. | Water-soluble manganese complex for selective electrocatalytic CO2 reduction to CO | |
| Di Giovanni et al. | Dinuclear cobalt complexes with a decadentate ligand scaffold: Hydrogen evolution and oxygen reduction catalysis | |
| Liu et al. | Ligand modification to stabilize the cobalt complexes for water oxidation | |
| Molnar et al. | Photochemical properties of mixed-metal supramolecular complexes | |
| Niu et al. | A noble-metal-free artificial photosynthesis system with TiO2 as electron relay for efficient photocatalytic hydrogen evolution | |
| Hoque et al. | Catalytic Oxidation of Water to Dioxygen by Mononuclear Ru Complexes Bearing a 2, 6‐Pyridinedicarboxylato Ligand | |
| JP7072797B2 (en) | Auxiliary catalyst for compounds and photocatalysts | |
| Wang et al. | A polypyridyl Co (ii) complex-based water reduction catalyst with double H 2 evolution sites | |
| Ho et al. | Cobalt complex of a tetraamido macrocyclic ligand as a precursor for electrocatalytic hydrogen evolution | |
| AU2005310262A1 (en) | Supramolecular complexes as photocatylysts for the production of hydrogen from water | |
| Yoshimura et al. | A systematic study on the double-layered photosensitizing dye structure on the surface of Pt-cocatalyst-loaded TiO2 nanoparticles | |
| EP2640733A1 (en) | Photosensitizers and use thereof for generating hydrogen from water |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A80 | Written request to apply exceptions to lack of novelty of invention |
Free format text: JAPANESE INTERMEDIATE CODE: A80 Effective date: 20180322 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20210113 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20211021 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20211101 |
|
| A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20211224 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20220217 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20220411 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20220425 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 7072797 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |