JP2003117402A - Photoreduction catalyst comprised of ruthenium polypyridine complex system - Google Patents
Photoreduction catalyst comprised of ruthenium polypyridine complex systemInfo
- Publication number
- JP2003117402A JP2003117402A JP2001321504A JP2001321504A JP2003117402A JP 2003117402 A JP2003117402 A JP 2003117402A JP 2001321504 A JP2001321504 A JP 2001321504A JP 2001321504 A JP2001321504 A JP 2001321504A JP 2003117402 A JP2003117402 A JP 2003117402A
- Authority
- JP
- Japan
- Prior art keywords
- complex
- polypyridine complex
- ruthenium
- catalyst system
- solvent
- 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.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 37
- 238000007540 photo-reduction reaction Methods 0.000 title claims abstract description 28
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 26
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 26
- 230000002378 acidificating effect Effects 0.000 claims abstract description 25
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 13
- 239000010941 cobalt Substances 0.000 claims abstract description 13
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 11
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 10
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 15
- 230000001603 reducing effect Effects 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 238000000034 method Methods 0.000 claims 5
- 238000007664 blowing Methods 0.000 claims 1
- 230000001678 irradiating effect Effects 0.000 claims 1
- 238000006722 reduction reaction Methods 0.000 abstract description 11
- 238000006243 chemical reaction Methods 0.000 description 16
- 229910002091 carbon monoxide Inorganic materials 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 239000012528 membrane Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 239000003504 photosensitizing agent Substances 0.000 description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229920000557 Nafion® Polymers 0.000 description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- -1 amine compound Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical class CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- 101100121112 Oryza sativa subsp. indica 20ox2 gene Proteins 0.000 description 1
- 101100121113 Oryza sativa subsp. japonica GA20OX2 gene Proteins 0.000 description 1
- 229910019891 RuCl3 Inorganic materials 0.000 description 1
- 235000002597 Solanum melongena Nutrition 0.000 description 1
- 244000061458 Solanum melongena Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 150000004700 cobalt complex Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】この発明は、ルテニウムポリ
ピリジン錯体から成る光還元触媒システムに関し、より
詳細には、ルテニウムポリピリジン錯体を担持させた強
酸性イオン交換高分子を含む光還元触媒系であって二酸
化炭素等の気相酸化物の還元に適した光還元触媒系に関
する。TECHNICAL FIELD The present invention relates to a photoreduction catalyst system comprising a ruthenium polypyridine complex, and more particularly to a photoreduction catalyst system comprising a strongly acidic ion exchange polymer carrying a ruthenium polypyridine complex. The present invention relates to a photoreduction catalyst system suitable for reducing gas phase oxides such as carbon dioxide.
【０００２】[0002]
【従来の技術】可視光領域に強い吸収を持つルテニウム
ポリピリジン錯体が光触媒（光増感剤）として作用し、
均一な有機溶媒中コバルト錯体へ電子を移動させ、二酸
化炭素を一酸化炭素へ還元することが知られている（R.
Ziessel et al., Helv. Chim.Acta, 60, 1065-1084 (1
986)）。しかしこの反応においては光増感剤、反応活性
点である錯体、最終的な還元剤である有機アミン化合物
が有機溶媒中に溶解し、かつ反応終了後には有機アミン
化合物の分解生成物も系中に残る。従って、光増感剤を
反応終了後に回収し再利用することが困難であり、実用
的なシステムとなっていない。また、金属錯体や酵素を
高分子に担持することはよく利用されている（J. Zhang
et al., Macromol. Symp., 105, 59-66 (1996); M. Ka
neko et al., Inorganic Chim. Acta, 44, L289-290 (1
980); 村橋俊介ら編著「高分子化学第4版」（共立出版
株式会社）126-131； 荻野一善ら編「高分子化学−基礎
と応用−第2版」（東京化学同人）200−203）が、これ
を二酸化炭素のような酸化物の還元に適用した例はな
い。2. Description of the Related Art A ruthenium polypyridine complex having strong absorption in the visible light region acts as a photocatalyst (photosensitizer),
It is known to transfer electrons to a cobalt complex in a homogeneous organic solvent to reduce carbon dioxide to carbon monoxide (R.
Ziessel et al., Helv. Chim. Acta, 60, 1065-1084 (1
986)). However, in this reaction, the photosensitizer, the complex that is the reaction active site, and the organic amine compound that is the final reducing agent are dissolved in the organic solvent, and after the reaction is completed, the decomposition products of the organic amine compound are also in the system. Remain in. Therefore, it is difficult to collect and reuse the photosensitizer after the reaction, which is not a practical system. In addition, it is often used to support metal complexes and enzymes on polymers (J. Zhang
et al., Macromol. Symp., 105, 59-66 (1996); M. Ka
neko et al., Inorganic Chim. Acta, 44, L289-290 (1
980); “Polymer Chemistry 4th Edition” edited by Shunsuke Murahashi (Kyoritsu Shuppan Co., Ltd.) 126-131; “Polymer Chemistry-Basics and Applications-Second Edition” edited by Kazuyoshi Ogino et al. ), But there is no example of applying it to the reduction of oxides such as carbon dioxide.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、このような
ルテニウムポリピリジン錯体を実用的な光還元触媒とし
て機能させる手段を提供することを目的とする。An object of the present invention is to provide a means for causing such a ruthenium polypyridine complex to function as a practical photoreduction catalyst.
【０００４】[0004]
【課題を解決するための手段及び発明の実施の形態】本
発明は、光増感剤であるルテニウムポリピリジン錯体を
実用的な反応系にすべく、ルテニウムポリピリジン錯体
を強酸性イオン交換高分子に担持した。このことによ
り、高価な光増感剤の取り扱いが容易になった。また、
これを担持した高分子を取り出し、光増感剤を繰り返し
使用することを可能にした。更に、反応の進行と共に、
光分解生成物等によって光増感剤の活性が低下するが、
これを担持した高分子を取り出した上で光増感剤を還元
してその活性を回復させることにより高価な光増感剤の
再利用をも可能にした。本発明の還元系は液相であるた
め、二酸化炭素や二酸化窒素などの気相酸化物の還元に
適している。BEST MODE FOR CARRYING OUT THE INVENTION In order to make a ruthenium polypyridine complex which is a photosensitizer into a practical reaction system, the present invention uses a ruthenium polypyridine complex as a strongly acidic ion exchange polymer. Supported on. This facilitated the handling of expensive photosensitizers. Also,
It was possible to take out the polymer carrying this and repeatedly use the photosensitizer. Furthermore, as the reaction progresses,
Although the activity of the photosensitizer decreases due to photodecomposition products,
It was also possible to reuse the expensive photosensitizer by taking out the polymer carrying this and then reducing the photosensitizer to restore its activity. Since the reduction system of the present invention is in the liquid phase, it is suitable for the reduction of gas phase oxides such as carbon dioxide and nitrogen dioxide.
【０００５】即ち、本発明は、ルテニウムポリピリジン
錯体を担持させた強酸性イオン交換高分子、コバルトポ
リピリジン錯体、及び溶媒から成る光還元触媒系であっ
て、該ルテニウムポリピリジン錯体及び該コバルトポリ
ピリジン錯体がそれぞれピリジン構造の窒素原子が６個
配位したルテニウム及びコバルトから成り、該強酸性イ
オン交換高分子がスルホン酸基を有し、該溶媒が２０重
量％以下の水を含んでもよい有機溶媒であり、該ルテニ
ウムポリピリジン錯体を担持させた強酸性イオン交換高
分子が該溶媒に浸され、該コバルトポリピリジン錯体が
該溶媒に溶解していることを特徴とする光還元触媒系で
ある。本発明のルテニウムポリピリジン錯体は、ピリジ
ン構造の窒素原子が６個配位したルテニウムから成る錯
体（以下「Ｒｕ錯体」ともいう。）であって、下記構造
を有する。That is, the present invention is a photoreduction catalyst system comprising a strongly acidic ion exchange polymer carrying a ruthenium polypyridine complex, a cobalt polypyridine complex, and a solvent, wherein the ruthenium polypyridine complex and the cobalt polypyridine complex are provided. An organic compound in which the pyridine complex is composed of ruthenium and cobalt each having six pyridine structure nitrogen atoms coordinated, the strongly acidic ion-exchange polymer has a sulfonic acid group, and the solvent may contain 20% by weight or less of water. A photoreduction catalyst system which is a solvent, wherein the strongly acidic ion exchange polymer carrying the ruthenium polypyridine complex is immersed in the solvent, and the cobalt polypyridine complex is dissolved in the solvent. . The ruthenium polypyridine complex of the present invention is a complex composed of ruthenium having a pyridine structure in which six nitrogen atoms are coordinated (hereinafter, also referred to as “Ru complex”) and has the following structure.
【化１】 [Chemical 1]
【０００６】この錯体は、溶液中でＲｕイオンとビピリ
ジンとを１：３のモル比で混合し、塩化物等の結晶とし
て得ることができる。強酸性イオン交換高分子は、スル
ホン酸基を有する高分子であれば特に制限はなく、高分
子としてはスチレン／ジビニルベンゼン、ポリヒドロキ
シアクリレート、ＰＶＡ、フッ素樹脂、特にパーフルオ
ロ樹脂などが挙げられる。このような強酸性イオン交換
高分子としては、ナフィオン（登録商標）などのスルホ
ン酸基を有するパーフッ素樹脂や、アンバーライト（登
録商標）などのスチレン系イオン交換樹脂などが好まし
い。強酸性イオン交換高分子中のスルホン酸基量は通常
１μ当量／ｇ〜２ｍ当量／ｇ、好ましくは、０．１〜
１．１ｍ当量／ｇである。This complex can be obtained as crystals of chloride or the like by mixing Ru ions and bipyridine in a solution at a molar ratio of 1: 3. The strongly acidic ion exchange polymer is not particularly limited as long as it is a polymer having a sulfonic acid group, and examples of the polymer include styrene / divinylbenzene, polyhydroxyacrylate, PVA, fluororesin, and particularly perfluororesin. As such a strongly acidic ion exchange polymer, a perfluororesin having a sulfonic acid group such as Nafion (registered trademark) and a styrene ion exchange resin such as Amberlite (registered trademark) are preferable. The amount of sulfonic acid group in the strongly acidic ion exchange polymer is usually 1 μeq / g to 2 meq / g, preferably 0.1 μeq / g.
It is 1.1 meq / g.
【０００７】Ｒｕ錯体を水に溶解させた水溶液に強酸性
イオン交換高分子を浸すことにより、Ｒｕ錯体を強酸性
イオン交換高分子に容易に担持させることができる。そ
の後このＲｕ錯体が担持した強酸性イオン交換高分子を
乾燥させてもよい。Ｒｕ錯体は強酸性イオン交換高分子
の有するスルホン酸基に１当量：１当量の比で吸着され
る。従って、Ｒｕ錯体は強酸性イオン交換高分子の有す
るスルホン酸基の全てに結合するわけではないが、後述
の理由からできるだけ全てのスルホン酸基に吸着されて
いることが好ましい。即ち、スルホン酸基に対するＲｕ
錯体量が０．７〜１．０当量／当量であることが好まし
い。By dipping the strongly acidic ion exchange polymer in an aqueous solution in which the Ru complex is dissolved in water, the Ru complex can be easily supported on the strongly acidic ion exchange polymer. Thereafter, the strongly acidic ion exchange polymer supported by this Ru complex may be dried. The Ru complex is adsorbed on the sulfonic acid group of the strongly acidic ion exchange polymer in a ratio of 1 equivalent: 1 equivalent. Therefore, the Ru complex does not bond to all the sulfonic acid groups of the strongly acidic ion exchange polymer, but it is preferable that the Ru complex be adsorbed to all sulfonic acid groups as much as possible for the reason described below. That is, Ru for the sulfonic acid group
The amount of complex is preferably 0.7 to 1.0 equivalent / equivalent.
【０００８】本発明のコバルトポリピリジン錯体は、ピ
リジン構造の窒素原子が６個配位したコバルトから成る
錯体（以下「Ｃｏ錯体」ともいう。）であって、下記構
造を有する。The cobalt polypyridine complex of the present invention is a complex composed of cobalt having a pyridine structure with six nitrogen atoms coordinated (hereinafter also referred to as "Co complex") and has the following structure.
【化２】 [Chemical 2]
【０００９】このＣｏ錯体は還元触媒系の溶媒に溶解し
ている。上記のように強酸性イオン交換高分子の有する
スルホン酸基にＲｕ錯体が結合するが、残余のスルホン
酸基にこの溶媒中のＣｏ錯体が吸着されるものと考えら
れる。しかし、このスルホン酸基に結合したＣｏ錯体は
還元作用に寄与しないと考えられる。溶媒中のＣｏ錯体
の量はＲｕ錯体とほぼ同モル数であることが好ましい。
従って、本発明の還元触媒系に投入するＣｏ錯体の量
は、Ｒｕ錯体に対して０．９〜１．１モル／モルである
ことが好ましい。This Co complex is dissolved in the solvent of the reduction catalyst system. As described above, the Ru complex binds to the sulfonic acid group of the strongly acidic ion exchange polymer, but it is considered that the Co complex in this solvent is adsorbed to the remaining sulfonic acid group. However, it is considered that the Co complex bonded to the sulfonic acid group does not contribute to the reducing action. The amount of Co complex in the solvent is preferably about the same as the number of moles of the Ru complex.
Therefore, the amount of the Co complex added to the reduction catalyst system of the present invention is preferably 0.9 to 1.1 mol / mol with respect to the Ru complex.
【００１０】本発明で用いる溶媒は、２０重量％以下、
好ましくは５重量％以下の水を含んでもよい、より好ま
しくは水を含まない有機溶媒である。水を含むとＲｕ錯
体が高分子から脱離してしまうおそれがあるからであ
る。有機溶媒としては、特に制限はなく、具体的には、
ＤＭＦ、アセトニトリル、トリエタノールアミン、トリ
エチルアミン、トリブチルアミン、トリプロピルアミ
ン、メチルジエタノールアミン、テトラメチルエチレン
ジアミン、エチレングリコールジメチルエーテル、ジオ
キサン等が挙げられるが、ＤＭＦ、アセトニトリル、ト
リエタノールアミンが好ましい。本発明の還元触媒系
は、これらＲｕ錯体を担持させた強酸性イオン交換高分
子、Ｃｏ錯体、及び溶媒から成る。Ｃｏ錯体が該溶媒に
溶解され、この溶媒にＲｕ錯体を担持させた強酸性イオ
ン交換高分子が浸されることにより、本発明の光還元触
媒系が構成される。The solvent used in the present invention is 20% by weight or less,
It is preferably an organic solvent which may contain 5% by weight or less of water, and more preferably contains no water. This is because the Ru complex may be desorbed from the polymer when it contains water. The organic solvent is not particularly limited, and specifically,
DMF, acetonitrile, triethanolamine, triethylamine, tributylamine, tripropylamine, methyldiethanolamine, tetramethylethylenediamine, ethylene glycol dimethyl ether, dioxane and the like can be mentioned, but DMF, acetonitrile and triethanolamine are preferable. The reduction catalyst system of the present invention comprises a strongly acidic ion exchange polymer carrying these Ru complexes, a Co complex, and a solvent. The photoreduction catalyst system of the present invention is constituted by dissolving the Co complex in the solvent and immersing the strongly acidic ion-exchange polymer supporting the Ru complex in the solvent.
【００１１】このように構成された光還元触媒系に可視
光及び／又は紫外光を照射する。本発明の光還元触媒系
の還元機構は下記のようであると考えられる（R. Ziess
el et al., Helv. Chim. Acta, 60, 1065-1084 (198
6)）。The photoreduction catalyst system thus constructed is irradiated with visible light and / or ultraviolet light. The reduction mechanism of the photoreduction catalyst system of the present invention is considered to be as follows (R. Ziess
el et al., Helv. Chim. Acta, 60, 1065-1084 (198
6)).
【化３】
即ち、Ｒｕ錯体が光エネルギーを吸収し、Ｃｏ錯体にこ
のエネルギーが移動して還元作用を行うものと考えられ
る。この還元機構の光源としては、可視光のみ若しくは
紫外光のみ又はこれら両方を含むものでもよいが、可視
光のみが好ましい。また、太陽光を用いてもよい。[Chemical 3] That is, it is considered that the Ru complex absorbs light energy, and this energy is transferred to the Co complex to perform a reducing action. The light source of the reduction mechanism may include only visible light, only ultraviolet light, or both, but only visible light is preferable. Alternatively, sunlight may be used.
【００１２】本発明の光還元触媒系は、酸化物を還元す
るのに適する。この酸化物としては気相であることが、
その扱いの観点から好ましく、二酸化炭素や二酸化窒素
がより好ましい。このような気体は本発明の光還元触媒
系の溶媒に、好ましくは飽和するまで、溶け込ませるこ
とにより容易に触媒と接触させて還元させることができ
る。The photoreduction catalyst system of the present invention is suitable for reducing oxides. The oxide is in the gas phase,
From the viewpoint of its handling, carbon dioxide and nitrogen dioxide are more preferable. Such a gas can be easily brought into contact with the catalyst for reduction by dissolving it in the solvent of the photoreduction catalyst system of the present invention, preferably until it is saturated.
【００１３】また、本発明の光還元触媒系は触媒（Ｒｕ
錯体）を回収して再利用することができる点に特徴があ
る。即ち、本発明の光還元触媒系により酸化物を還元し
た後に、この光還元触媒系からＲｕ錯体を担持させた強
酸性イオン交換高分子を取り出して洗浄し、該光還元触
媒系に戻すことにより、触媒を回収して再利用すること
が可能であり、これにより酸化物を連続的に還元するこ
とができる。この洗浄は通常水で行うが、酸の水溶液を
用いて行ってもよい。但し、あまり強い酸（例えば、酸
の濃度が１規定以上）を用いるとＲｕ錯体が高分子から
脱離してしまうので好ましくない。Ｒｕ錯体を洗浄する
際又はその前後に、適当な手段によりＲｕ錯体を還元す
ればなお効果的に触媒を再利用することができるので好
ましい。Further, the photoreduction catalyst system of the present invention is a catalyst (Ru
The feature is that the complex) can be recovered and reused. That is, after reducing the oxide by the photoreduction catalyst system of the present invention, the strongly acidic ion exchange polymer carrying the Ru complex is taken out from the photoreduction catalyst system, washed, and returned to the photoreduction catalyst system. The catalyst can be recovered and reused, which allows the oxide to be continuously reduced. This washing is usually performed with water, but an aqueous solution of acid may be used. However, it is not preferable to use a too strong acid (for example, the acid concentration is 1 N or more) because the Ru complex is desorbed from the polymer. It is preferable to reduce the Ru complex by an appropriate means during or before and after washing the Ru complex, because the catalyst can be reused more effectively.
【００１４】[0014]
【実施例】以下、実施例にて本発明を例証するが、本発
明を限定することを意図するものではない。製造例１
RuCl3水和物（和光純薬製）4.4 mmol及びビピリジン(2,
2’-bipyridine)（関東化学製）13.2 mmolをDMF（和光
純薬製、特級） 50 mlに加え、120 ℃で3時間攪拌す
る。室温まで冷却後、溶液量が10 ml以下になるまで溶
媒を留去し、その溶液にテトラn-ブチルアンモニウムク
ロリド（関東化学製）の飽和アセトン溶液を加え、析出
した橙赤色の沈殿をろ取する。析出した固体をメタノー
ルで再結晶することにより橙赤色固体であるＲｕ錯体の
塩化物（化４）を得た。EXAMPLES The present invention will be illustrated below with reference to Examples.
It is not intended to limit the light.Production example 1
RuCl3Hydrate (Wako Pure Chemical Industries, Ltd.) 4.4 mmol and bipyridine (2,
2'-bipyridine) (Kanto Kagaku) 13.2 mmol DMF (Wako
(Pure drug, special grade) Add to 50 ml and stir at 120 ℃ for 3 hours.
It After cooling to room temperature, dissolve the solution until the volume becomes 10 ml or less.
The medium is distilled off and the solution is treated with tetra-n-butylammonium chloride.
Saturated acetone solution of Lolid (Kanto Kagaku) was added and precipitated
The orange-red precipitate formed is collected by filtration. The deposited solid is methanol
Of the Ru complex which is an orange-red solid by recrystallizing
Chloride (Chemical Formula 4) was obtained.
【化４】 [Chemical 4]
【００１５】製造例２
CoCl2水和物（和光純薬製）1 mmol及びビピリジン(2,
2’-bipyridine)（関東化学製）3 mmolをエタノールに
溶解させ、８０℃で２時間攪拌する。エタノールを減圧
留去することにより、淡黄色固体であるＣｏ錯体の塩化
物（化５）を得た。[0015]Production example 2
CoCl2Hydrate (Wako Pure Chemical Industries, Ltd.) 1 mmol and bipyridine (2,
2'-bipyridine) (Kanto Kagaku) 3 mmol in ethanol
Dissolve and stir at 80 ° C. for 2 hours. Depressurize ethanol
By distilling off, the chlorination of the Co complex, which is a pale yellow solid
The compound (Chemical Formula 5) was obtained.
【化５】 [Chemical 5]
【００１６】参考例１
これらＲｕ錯体15 μmolとＣｏ錯体15 μmolとを溶媒
（DMF/TEOA(還元剤)(4/1v/v)）30 mlに溶解させた。こ
の溶媒を図1に示す装置のガラスセルに入れ、系内の雰
囲気をＣＯ２で置換し、Ｘｅランプにより照射した。後
述の実施例と同様にして生成したＣＯ及びＨ２と測定し
た。その照射時間との関係を表１に示す。[0016]Reference example 1
These Ru complex (15 μmol) and Co complex (15 μmol) are used as a solvent.
It was dissolved in 30 ml of (DMF / TEOA (reducing agent) (4/1 v / v)). This
Put the solvent in the glass cell of the device shown in Fig. 1 into the atmosphere of the system.
The atmosphere is COTwoAnd was irradiated with a Xe lamp. rear
CO and H produced in the same manner as in the above-mentioned examplesTwoAnd measured
It was Table 1 shows the relationship with the irradiation time.
【表１】
これらの触媒が二酸化炭素を一酸化炭素に還元している
ことが確認された。なお、水素は上述の機構（化３）に
より発生したものと考えられ、その発生は本発明の錯体
が還元機能を有することを示している。[Table 1] It was confirmed that these catalysts reduced carbon dioxide to carbon monoxide. Hydrogen is considered to be generated by the above mechanism (Chemical Formula 3), and the generation thereof indicates that the complex of the present invention has a reducing function.
【００１７】実施例１
（１）スルホン酸基を有する高分子膜（デュポン製 NF
112）(50 mg)をＲｕ錯体（15 μmol）の水溶液に浸し、
錯体を吸着させた後、乾燥させた。この水溶液中にＲｕ
が確認されなかったことから、この高分子膜の有するス
ルホン酸基にほぼ全てに対してＲｕ錯体が１モル吸着し
ているものと考えられる。
（２）溶媒（DMF/TEOA(還元剤)(4/1 v/v)）30 mlを、ボ
ンベから先端に注射針を付けたゴム管で30分以上CO2を
直接導入して飽和させた。
（３）（１）と（２）で準備した溶媒、膜、及びＣｏ錯
体(15 μmol)を用いて、図1に示す装置を組み、系内の
雰囲気をＣＯ２で置換した。
（４）Ｘｅランプにより照射した。[0017]Example 1
(1) Polymer film having sulfonic acid group (NF made by DuPont
112) (50 mg) was immersed in an aqueous solution of Ru complex (15 μmol),
After adsorbing the complex, it was dried. Ru in this aqueous solution
Since it was not confirmed that the polymer film has
1 mol of Ru complex was adsorbed to almost all of the rufonic acid groups.
It is considered that
(2) Add 30 ml of solvent (DMF / TEOA (reducing agent) (4/1 v / v)) to the
Use a rubber tube with an injection needle at the tip from the container for 30 minutes or more CO2To
Directly introduced and saturated.
(3) Solvent, film, and Co complex prepared in (1) and (2)
Using the body (15 μmol), the device shown in Fig. 1 was assembled and
CO atmosphereTwoReplaced with.
(4) Irradiation with a Xe lamp.
【００１８】（５）ガラスセルから反応ガスを所定時間
ごとに少量ずつ回収し分析した。シリンジ部を10回交互
に動かし、気相を均一にする。セプタム部位からガスタ
イトシリンジを挿入し、シリンジ内を反応系内の気体で
置換する。次にそのガスタイトシリンジを用いて、系内
の気相を30μl採取する。採取したガスをそのままガス
クロマトグラフィーに導入し、Ｈ２、ＣＯ、Ｎ２、
Ｏ２、ＣＯ２を分離検出する。予め作成した検量線を用
いて、0.3 ml 中のＣＯ及びＨ２の総量（mol数）を算出
し、その時間における系内の気相の各成分総量を求め
る。ガスクロマトグラフィー分析は下記条件で行った。
・装置−HITACHI 263-50 Gas Chromatograph
・検出器−TCD（熱伝導度検出器）
・カラム−活性炭［ガラスカラム5 mm(外径)×3 mm(内
径)×3 m(長さ)］
・キャリアーガス−アルゴン
・流速−30 ml / min
・温度−カラム（70℃）、検出器（80℃）、導入部（80
℃）(5) The reaction gas was collected from the glass cell little by little at predetermined time intervals and analyzed. Alternately move the syringe part 10 times to make the gas phase uniform. A gas tight syringe is inserted from the septum site, and the inside of the syringe is replaced with the gas in the reaction system. Next, 30 μl of the gas phase in the system is sampled using the gas tight syringe. The collected gas is directly introduced into gas chromatography, and H 2 , CO, N 2 ,
Separately detect O 2 and CO 2 . Using a calibration curve prepared in advance, the total amount of CO and H 2 (mol number) in 0.3 ml is calculated, and the total amount of each component of the gas phase in the system at that time is calculated. Gas chromatography analysis was performed under the following conditions.・ Device-HITACHI 263-50 Gas Chromatograph ・ Detector-TCD (thermal conductivity detector) ・ Column-activated carbon [glass column 5 mm (outer diameter) × 3 mm (inner diameter) × 3 m (length)] ・ Carrier Gas-argon-Flow rate-30 ml / min-Temperature-column (70 ° C), detector (80 ° C), inlet (80
℃)
【００１９】（６）反応の停止を確認したら、膜のみを
反応系から取出し、その膜を１規定塩酸、水に順に浸し
て洗浄した後、乾燥した。
（７）膜のみを再利用し上記（３）〜（６）を４回繰り
返した。生成したＣＯ及びＨ２と照射時間との関係を表
２及び図２に示す。(6) After confirming the termination of the reaction, only the membrane was taken out from the reaction system, and the membrane was immersed in 1N hydrochloric acid and water in that order for washing, and then dried. (7) Only the membrane was reused, and the above (3) to (6) were repeated 4 times. The relationship between the generated CO and H 2 and the irradiation time is shown in Table 2 and FIG.
【表２】 [Table 2]
【００２０】実施例２
実施例１と同様に（１）〜（５）の工程を行った。その
後、反応系内から溶媒及び膜を取出し、ナス型フラスコ
に移す。減圧下、超音波を用いて脱気を行う。その後膜
に実施例１の（６）の工程を行う。脱気した溶媒を入れ
た容器にＣＯ２を約40分間吹き込み、溶液を再度ＣＯ２
で飽和する。このようにして準備した反応溶液と膜を用
いて実施例１の（３）〜（６）を４回繰り返した。生成
したＣＯ及びＨ２と照射時間との関係を表３及び図３に
示す。[0020]Example 2
The steps (1) to (5) were performed in the same manner as in Example 1. That
After that, take out the solvent and the membrane from the reaction system and put them in an eggplant type flask.
Move to. Degas using ultrasonic waves under reduced pressure. Then the membrane
Then, the step (6) of Example 1 is performed. Add degassed solvent
CO in the containerTwoBubbling for about 40 minutes and re-dosing the solution with COTwo
Is saturated with. Use the reaction solution and membrane prepared in this way.
Then, (3) to (6) of Example 1 were repeated four times. Generate
CO and HTwoTable 3 and Fig. 3 show the relationship between irradiation time and irradiation time.
Show.
【表３】 [Table 3]
【００２１】実施例３
高分子膜を高分子ビーズ（シグマ-アルドリッチ製 Naf
ion NR50）に置き替えて実施例２と同様の操作を行っ
た。生成したＣＯ及びＨ２と照射時間との関係を表４及
び図４に示す。[0021]Example 3
Polymer beads with polymer beads (Sigma-Aldrich Naf
ion NR50) and perform the same operation as in Example 2.
It was CO and H generatedTwoAnd the relationship between irradiation time and Table 4
And shown in FIG.
【表４】
本実施例にてナフィオンビーズを用いた場合は、実施例
１、２のようにナフィオン膜を用いた場合に比較して、
吸着した錯体への光のあたり方が均一でないために全体
的な反応効率の低下につながったと考えられる。[Table 4] In the case of using Nafion beads in this example, compared to the case of using a Nafion membrane as in Examples 1 and 2,
It is considered that the overall reaction efficiency was lowered because the light adhering to the adsorbed complex was not uniform.
【００２２】実施例４
実施例１と同様に（１）〜（５）の工程を行った。その
後、反応系のすべてのもの（反応溶液及び膜）を洗浄等
せずに、そのままナス型フラスコに移し、減圧下、超音
波を用いて脱気を行った。脱気した反応溶液及び膜を入
れた容器にＣＯ２を約40分間吹き込み、溶液を再度ＣＯ
２で飽和させた。このようにして準備した反応溶液と膜
を用いて実施例１の（３）〜（６）を４回繰り返した。
生成したＣＯ及びＨ２と照射時間との関係を表５及び図
５に示す。[0022]Example 4
The steps (1) to (5) were performed in the same manner as in Example 1. That
After that, wash everything in the reaction system (reaction solution and membrane), etc.
Without moving, transfer it to an eggplant-shaped flask as it is, and under reduced pressure, supersonic
Degassing was done using waves. Insert the degassed reaction solution and membrane
CO in the containerTwoBubbling for about 40 minutes and re-dosing the solution with CO
TwoSaturated with. Reaction solution and membrane prepared in this way
Was used to repeat (3) to (6) of Example 1 four times.
CO and H generatedTwoAnd the relationship between irradiation time and table 5 and figure
5 shows.
【表５】 [Table 5]
【００２３】[0023]
【発明の効果】以上の実施例から、Ｒｕ錯体を高分子膜
に固定した本発明の光還元触媒系を用いることにより、
気相酸化物を効果的に還元することができる。更に、こ
のような構成をとることにより、Ｒｕ触媒の再利用が可
能になり、触媒としての寿命、すなわち総反応時間が伸
び、還元生成物の総生成量が増えた。From the above examples, by using the photoreduction catalyst system of the present invention in which the Ru complex is immobilized on the polymer membrane,
The vapor phase oxide can be effectively reduced. Furthermore, by adopting such a configuration, the Ru catalyst can be reused, the life as a catalyst, that is, the total reaction time is extended, and the total amount of reduction products is increased.
【図１】実施例で用いた光還元反応を行うための装置を
示す図である。FIG. 1 is a diagram showing an apparatus for performing a photoreduction reaction used in Examples.
【図２】実施例１にて生成したＣＯ及びＨ２と照射時間
との関係を示す図である。FIG. 2 is a diagram showing a relationship between CO and H 2 generated in Example 1 and irradiation time.
【図３】実施例２にて生成したＣＯ及びＨ２と照射時間
との関係を示す図である。FIG. 3 is a diagram showing a relationship between CO and H 2 generated in Example 2 and irradiation time.
【図４】実施例３にて生成したＣＯ及びＨ２と照射時間
との関係を示す図である。FIG. 4 is a diagram showing a relationship between CO and H 2 generated in Example 3 and irradiation time.
【図５】実施例４にて生成したＣＯ及びＨ２と照射時間
との関係を示す図である。FIG. 5 is a diagram showing a relationship between CO and H 2 generated in Example 4 and irradiation time.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4G069 AA03 AA06 AA10 BA23A BA24B BA27A BA27B BA48A BC67A BC67B BC70A BC70B BE16A BE38A CC40 EC27 GA09 GA20 ─────────────────────────────────────────────────── ─── Continued front page F-term (reference) 4G069 AA03 AA06 AA10 BA23A BA24B BA27A BA27B BA48A BC67A BC67B BC70A BC70B BE16A BE38A CC40 EC27 GA09 GA20
Claims (6)
た強酸性イオン交換高分子、コバルトポリピリジン錯
体、及び溶媒から成る光還元触媒系であって、該ルテニ
ウムポリピリジン錯体及び該コバルトポリピリジン錯体
がそれぞれピリジン構造の窒素原子が６個配位したルテ
ニウム及びコバルトから成り、該強酸性イオン交換高分
子がスルホン酸基を有し、該溶媒が２０重量％以下の水
を含んでもよい有機溶媒であり、該ルテニウムポリピリ
ジン錯体を担持させた強酸性イオン交換高分子が該溶媒
に浸され、該コバルトポリピリジン錯体が該溶媒に溶解
していることを特徴とする光還元触媒系。1. A photoreduction catalyst system comprising a strongly acidic ion-exchange polymer supporting a ruthenium polypyridine complex, a cobalt polypyridine complex, and a solvent, wherein the ruthenium polypyridine complex and the cobalt polypyridine complex are respectively An organic solvent which comprises ruthenium and cobalt in which 6 nitrogen atoms of a pyridine structure are coordinated, the strongly acidic ion exchange polymer has a sulfonic acid group, and the solvent may contain 20% by weight or less of water, A photoreduction catalyst system, wherein the strongly acidic ion exchange polymer carrying the ruthenium polypyridine complex is immersed in the solvent, and the cobalt polypyridine complex is dissolved in the solvent.
ルホン酸基量が１μ当量／ｇ〜２ｍ当量／ｇであり、該
スルホン酸基に対する前記ルテニウムポリピリジン錯体
量が０．７〜１．０当量／当量であり、該ルテニウムポ
リピリジン錯体に対するコバルトポリピリジン錯体量が
０．９〜１．１モル／モルである請求項１に記載の光還
元触媒系。2. The amount of the sulfonic acid group in the strongly acidic ion exchange polymer is 1 μeq / g to 2 meq / g, and the amount of the ruthenium polypyridine complex relative to the sulfonic acid group is 0.7 to 1. The photoreduction catalyst system according to claim 1, wherein the amount is 0 equivalent / equivalent, and the amount of the cobalt polypyridine complex relative to the ruthenium polypyridine complex is 0.9 to 1.1 mol / mol.
可視光及び／又は紫外光を照射して、酸化物を還元する
方法。3. A method for reducing an oxide by irradiating the photoreduction catalyst system according to claim 1 with visible light and / or ultraviolet light.
還元触媒系に該二酸化炭素を吹き込むことにより該光還
元触媒系に該二酸化炭素を飽和させた後に該光還元触媒
系に可視光及び／又は紫外光を照射する請求項３に記載
の方法。4. The oxide is carbon dioxide, and the photoreduction catalyst system is saturated with the carbon dioxide by blowing the carbon dioxide into the photoreduction catalyst system. The method according to claim 3, wherein the ultraviolet light is irradiated.
元した後に、前記光還元触媒系から前記ルテニウムポリ
ピリジン錯体を担持させた強酸性イオン交換高分子を取
り出して洗浄し、該光還元触媒系に戻すことから成る、
酸化物を連続的に還元する方法。5. After reducing the oxide by the method according to claim 3 or 4, the strongly acidic ion-exchange polymer carrying the ruthenium polypyridine complex is taken out from the photoreduction catalyst system and washed to obtain the photoreduction. Consisting of returning to the catalyst system,
A method of continuously reducing oxides.
する際又はその前後に該ルテニウムポリピリジン錯体を
還元する請求項５に記載の方法。6. The method according to claim 5, wherein the ruthenium polypyridine complex is reduced before or after washing the ruthenium polypyridine complex.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001321504A JP3860008B2 (en) | 2001-10-19 | 2001-10-19 | Photoreduction catalyst system composed of ruthenium polypyridine complex |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001321504A JP3860008B2 (en) | 2001-10-19 | 2001-10-19 | Photoreduction catalyst system composed of ruthenium polypyridine complex |
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| JP3860008B2 JP3860008B2 (en) | 2006-12-20 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006346639A (en) * | 2005-06-20 | 2006-12-28 | National Institutes Of Natural Sciences | Photochemically reproducible catalyst and reducing method of organic compound using the same |
| WO2012063697A1 (en) * | 2010-11-12 | 2012-05-18 | 富士フイルム株式会社 | Co production method and device for same |
| CN114392774A (en) * | 2022-01-28 | 2022-04-26 | 合肥工业大学 | Preparation method of polymer supported synergistic catalyst and application of polymer supported synergistic catalyst in carbon dioxide photoreduction catalysis |
| CN115806677A (en) * | 2022-11-15 | 2023-03-17 | 广东工业大学 | Ruthenium polymer with photo-thermal conversion performance and preparation method thereof |
-
2001
- 2001-10-19 JP JP2001321504A patent/JP3860008B2/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006346639A (en) * | 2005-06-20 | 2006-12-28 | National Institutes Of Natural Sciences | Photochemically reproducible catalyst and reducing method of organic compound using the same |
| WO2012063697A1 (en) * | 2010-11-12 | 2012-05-18 | 富士フイルム株式会社 | Co production method and device for same |
| JP2012101986A (en) * | 2010-11-12 | 2012-05-31 | Fujifilm Corp | Co production method and device for same |
| CN114392774A (en) * | 2022-01-28 | 2022-04-26 | 合肥工业大学 | Preparation method of polymer supported synergistic catalyst and application of polymer supported synergistic catalyst in carbon dioxide photoreduction catalysis |
| CN114392774B (en) * | 2022-01-28 | 2024-01-23 | 湖南天氟新材料有限公司 | Preparation method of polymer supported synergistic catalyst and application of polymer supported synergistic catalyst in carbon dioxide photo-reduction catalysis |
| CN115806677A (en) * | 2022-11-15 | 2023-03-17 | 广东工业大学 | Ruthenium polymer with photo-thermal conversion performance and preparation method thereof |
| CN115806677B (en) * | 2022-11-15 | 2023-09-01 | 广东工业大学 | Ruthenium polymer with photo-thermal conversion performance and preparation method thereof |
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| Publication number | Publication date |
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| JP3860008B2 (en) | 2006-12-20 |
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