JP2003275599A - Composite photocatalyst for reducing carbon dioxide and carbon dioxide photo-reducing method using the same - Google Patents
Composite photocatalyst for reducing carbon dioxide and carbon dioxide photo-reducing method using the sameInfo
- Publication number
- JP2003275599A JP2003275599A JP2002076830A JP2002076830A JP2003275599A JP 2003275599 A JP2003275599 A JP 2003275599A JP 2002076830 A JP2002076830 A JP 2002076830A JP 2002076830 A JP2002076830 A JP 2002076830A JP 2003275599 A JP2003275599 A JP 2003275599A
- Authority
- JP
- Japan
- Prior art keywords
- carbon dioxide
- photocatalyst
- composite
- dioxide reduction
- composite photocatalyst
- 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
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 60
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 60
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 40
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- 239000004065 semiconductor Substances 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 238000006722 reduction reaction Methods 0.000 claims description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 16
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 12
- 239000010936 titanium Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910021536 Zeolite Inorganic materials 0.000 claims description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 7
- 239000010457 zeolite Substances 0.000 claims description 7
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 6
- 235000019253 formic acid Nutrition 0.000 claims description 6
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910000510 noble metal Inorganic materials 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 238000007540 photo-reduction reaction Methods 0.000 claims 2
- 230000001699 photocatalysis Effects 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000012494 Quartz wool Substances 0.000 description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 239000012153 distilled water Substances 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000010453 quartz Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000007872 degassing Methods 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000003622 immobilized catalyst Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000011358 absorbing material Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical class [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910002367 SrTiO Inorganic materials 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012806 monitoring device Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 229910052700 potassium Chemical class 0.000 description 2
- 239000011591 potassium Chemical class 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- ZFYIQPIHXRFFCZ-QMMMGPOBSA-N (2s)-2-(cyclohexylamino)butanedioic acid Chemical compound OC(=O)C[C@@H](C(O)=O)NC1CCCCC1 ZFYIQPIHXRFFCZ-QMMMGPOBSA-N 0.000 description 1
- 101100000419 Autographa californica nuclear polyhedrosis virus AC41 gene Proteins 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate trihydrate Substances [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000013480 data collection Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- -1 etc. Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、太陽光を利用して
反応を行わせ、有用な化合物を製造するための新規な複
合光触媒及びそれを用いて水と二酸化炭素から各種の有
機化合物を製造する方法に関するものである。TECHNICAL FIELD The present invention relates to a novel composite photocatalyst for producing a useful compound by carrying out a reaction using sunlight, and a variety of organic compounds produced from water and carbon dioxide using the same. It is about how to do it.
【０００２】[0002]
【従来の技術】化石燃料の大量消費による埋蔵量の枯渇
とともに、その燃料に伴う大気中の二酸化炭素濃度の急
速な増加が地球の温暖化、海面の上昇、異常気象の面で
大きな社会問題となってきている。そのため、最近、化
石燃料に代わるべきエネルギー源として太陽光の有効利
用方法とともに、二酸化炭素の有用資源化についての研
究が盛んに行われている。2. Description of the Related Art With the depletion of reserves due to the large consumption of fossil fuels, the rapid increase in the carbon dioxide concentration in the atmosphere due to the fuels has become a major social problem in terms of global warming, sea level rise, and abnormal weather. It has become to. Therefore, recently, researches on effective utilization of sunlight as an energy source that should replace fossil fuels and the utilization of carbon dioxide as a useful resource have been actively conducted.
【０００３】そして、これまで二酸化炭素を還元固定化
し、炭素源として利用する方法としては、鉄系又は銅系
の二酸化炭素還元触媒の存在下に水素を暗反応させてメ
タン、メチルアルコールを生成させる接触水素化固定化
法、有機化合物例えばサリチル酸合成の際の反応体とし
て二酸化炭素を利用する有機化学的固定化法、金属電極
上で水を電気分解し、発生する水素を還元剤として二酸
化炭素を還元して、ギ酸、アルデヒド、炭化水素などを
生成させる電気化学的固定化法、半導体光触媒を用い、
光照射によりメタン、メチルアルコールを生成させる光
触媒的固定化方法などが知られている。As a method of reducing and fixing carbon dioxide and utilizing it as a carbon source, hydrogen is darkly reacted in the presence of an iron-based or copper-based carbon dioxide reduction catalyst to produce methane and methyl alcohol. Catalytic hydrogenation immobilization method, organic chemical immobilization method that uses carbon dioxide as a reactant in the synthesis of salicylic acid, for example, electrolysis of water on a metal electrode, and hydrogen generated is converted to carbon dioxide as a reducing agent. Using an electrochemical immobilization method to reduce formic acid, aldehydes, hydrocarbons, etc., semiconductor photocatalyst,
A photocatalytic immobilization method in which methane and methyl alcohol are generated by light irradiation is known.
【０００４】これらの方法は、多量のエネルギーを消費
せずにクリーンな条件下で二酸化炭素を固定化できる点
では非常に好ましいものといえるが、生成効率の点で問
題があり、実用化するにはまだ十分満足すべきものとは
いえない。Although these methods can be said to be very preferable in that carbon dioxide can be immobilized under clean conditions without consuming a large amount of energy, they have a problem in production efficiency, and are practically used. Is not yet very satisfactory.
【０００５】他方、ＴｉＯ2、ＺｎＯ、ＣｄＳ、Ｇａ
Ｐ、ＳｉＣ、ＳｒＴｉＯ3などの半導体触媒の粉末を水
に懸濁させ、二酸化炭素を通しながらキセノンランプや
高圧水銀灯のような人工光源からの光照射を行うと、ホ
ルムアルデヒド、ギ酸、メタン、メチルアルコールなど
が生成すること［「ネイチュア（Ｎａｔｕｒｅ）」，第
２７７巻，第６３７〜６３８ページ（１９７９）］、こ
の際半導体光触媒に貴金属を添加すれば活性が向上する
こと［「触媒」，第３９巻，第２４〜３１ページ（１９
９７）、「キャタリスト・トゥデイ（Ｃａｔａｌｙｓｔ
Ｔｏｄａｙ）」，第３９巻，第１６９〜１７５ページ
（１９９７）］が知られている。On the other hand, TiO 2 , ZnO, CdS, Ga
When a powder of semiconductor catalyst such as P, SiC, SrTiO 3 is suspended in water and light is emitted from an artificial light source such as a xenon lamp or a high pressure mercury lamp while passing carbon dioxide, formaldehyde, formic acid, methane, methyl alcohol are obtained. And the like [“Nature”, vol. 277, pp. 637-638 (1979)], and the activity is improved by adding a noble metal to the semiconductor photocatalyst at this time [“catalyst”, vol. 39]. , Pages 24-31 (19
97), "Catalyst Today (Catalyst
Today, "39, 169-175 (1997)].
【０００６】ところで、このような光触媒反応は、光照
射により半導体表面に生成する電子と正孔の高い還元力
及び酸化力を利用する反応であるが、この際ある種の半
導体光触媒を用いると水を水素と酸素に分解して、この
水素を二酸化炭素の還元剤として使用することができる
ので、この場合には、前記した接触水素化固定化法を利
用することが可能になる。By the way, such a photocatalytic reaction is a reaction utilizing the high reducing power and oxidizing power of electrons and holes generated on the semiconductor surface by light irradiation. At this time, when a certain kind of semiconductor photocatalyst is used, water is used. Can be decomposed into hydrogen and oxygen, and this hydrogen can be used as a reducing agent for carbon dioxide. In this case, therefore, the above-mentioned catalytic hydrogenation immobilization method can be used.
【０００７】したがって、このようにして二酸化炭素を
メタン、メチルアルコールなどに変換できれば、高効率
の燃料を得ることができ、また人工光源に代えて太陽光
を用いれば、さらにエネルギーの有効利用をはかること
ができるにもかかわらず、これまでこのような試みは全
くなされていなかった。Therefore, if carbon dioxide can be converted into methane, methyl alcohol, etc. in this way, a highly efficient fuel can be obtained, and if sunlight is used instead of the artificial light source, more effective use of energy can be achieved. Despite being able to do so, no such attempt has been made so far.
【０００８】[0008]
【発明が解決しようとする課題】本発明は、このような
事情のもとで、太陽光をエネルギー源とし、効率よく二
酸化炭素を還元して有用な化合物を生成するための新規
な触媒を提供することを目的としてなされたものであ
る。Under the circumstances, the present invention provides a novel catalyst for efficiently reducing carbon dioxide by using sunlight as an energy source to produce a useful compound. It was made for the purpose of doing.
【０００９】[0009]
【課題を解決するための手段】本発明者らは、太陽光を
用いて二酸化炭素を有用な化合物に変換するための方法
について鋭意研究を重ねた結果、半導体光触媒と二酸化
炭素還元触媒とを複合化した新規な触媒を用いることに
より、その目的を達成しうることを見出し、この知見に
基づいて本発明をなすに至った。Means for Solving the Problems As a result of intensive studies on the method for converting carbon dioxide into a useful compound by using sunlight, the present inventors have combined a semiconductor photocatalyst and a carbon dioxide reduction catalyst. It was found that the object can be achieved by using the modified novel catalyst, and the present invention has been completed based on this finding.
【００１０】すなわち、本発明は、半導体光触媒成分と
二酸化炭素還元触媒成分との複合化物から成る二酸化炭
素還元用複合光触媒、及びこの複合光触媒の存在下で、
水と二酸化炭素の混合物に太陽光を照射し、ホルムアル
デヒド、ギ酸、メタン、メチルアルコール及びエチルア
ルコールの中から選ばれる少なくとも１種の化合物を生
成させることを特徴とする二酸化炭素光還元方法を提供
するものである。That is, the present invention provides a composite photocatalyst for carbon dioxide reduction comprising a composite of a semiconductor photocatalyst component and a carbon dioxide reduction catalyst component, and in the presence of this composite photocatalyst,
A method for photoreducing carbon dioxide, which comprises irradiating a mixture of water and carbon dioxide with sunlight to produce at least one compound selected from formaldehyde, formic acid, methane, methyl alcohol and ethyl alcohol. It is a thing.
【００１１】[0011]
【発明の実施の形態】本発明の複合光触媒は、半導体光
触媒成分と二酸化炭素還元触媒成分とから構成されてい
るが、この半導体光触媒成分としては、これまで二酸化
炭素に光照射して、メタンやメチルアルコールとして固
定化する際に使用されていた公知の半導体光触媒の中か
ら任意に選んで用いることができる。このような半導体
光触媒としては、例えば、ＴｉＯ2、ＺｎＯ、ＣｄＳ、
ＧａＰ、ＳｉＣ、ＳｒＴｉＯ3などが知られているが、
特に、Ｎａ2Ｔｉ6Ｏ13、Ｋ2Ｔｉ6Ｏ13、ＫＴｉＮｂＯ5
などのチタン系複合酸化物が、太陽光照射下での水素発
生率が高く、二酸化炭素の還元効率が高いので好まし
い。BEST MODE FOR CARRYING OUT THE INVENTION The composite photocatalyst of the present invention is composed of a semiconductor photocatalyst component and a carbon dioxide reduction catalyst component. It can be arbitrarily selected from known semiconductor photocatalysts used for immobilization as methyl alcohol. Examples of such semiconductor photocatalysts include TiO 2 , ZnO, CdS,
GaP, SiC, SrTiO 3 and the like are known,
In particular, Na 2 Ti 6 O 13 , K 2 Ti 6 O 13 , KTiNbO 5
Titanium-based composite oxides such as are preferable because they have a high hydrogen generation rate under sunlight irradiation and a high carbon dioxide reduction efficiency.
【００１２】また、半導体光触媒には所望に応じ助触媒
として貴金属、例えば白金、ニッケル、ルテニウム、ロ
ジウム、パラジウム又はそれらの酸化物などを担持させ
て、光触媒活性を向上させることができる。この貴金属
の担持量としては、半導体光触媒全質量に基づき、０．
１〜１．０質量％、好ましくは０．２〜０．４質量％の
範囲で選ばれる。If desired, the semiconductor photocatalyst may be loaded with a noble metal such as platinum, nickel, ruthenium, rhodium, palladium or an oxide thereof as a co-catalyst to improve the photocatalytic activity. The amount of the noble metal supported is 0.
It is selected in the range of 1 to 1.0% by mass, preferably 0.2 to 0.4% by mass.
【００１３】半導体光触媒に貴金属を担持させるのは、
常法に従い、例えばチタン系複合酸化物粒体に、貴金属
可溶性塩の溶液を含浸させ、乾燥後焼成するか、貴金属
可溶性塩の溶液にチタン系複合酸化物粒子を分散させ、
光を照射して粒子表面に助触媒の金属を沈積させること
によって用うことができる。後者は助触媒として特に白
金族金属を担持させる場合に有利である。この半導体光
触媒成分は、通常、粉砕して０．１〜５．０μｍの粉末
として用いられる。この半導体光触媒は、光照射により
半導体表面に生成する電子と正孔の高い還元力及び酸化
力を生じ、これを利用して水を水素と酸素に分解する作
用を有する。Supporting a noble metal on a semiconductor photocatalyst is
According to a conventional method, for example, titanium-based composite oxide particles, impregnated with a solution of a noble metal-soluble salt, and dried or baked, or dispersed titanium-based composite oxide particles in a solution of a noble metal-soluble salt,
It can be used by irradiating light to deposit the metal of the promoter on the surface of the particles. The latter is advantageous especially when a platinum group metal is supported as a cocatalyst. This semiconductor photocatalyst component is usually pulverized and used as a powder of 0.1 to 5.0 μm. This semiconductor photocatalyst has a function of generating high reducing power and oxidizing power of electrons and holes generated on a semiconductor surface by light irradiation, and utilizing this, water is decomposed into hydrogen and oxygen.
【００１４】次に、二酸化炭素還元触媒成分としては、
これまで知られている鉄系二酸化炭素還元触媒や銅系二
酸化炭素還元触媒や、これらの触媒を高い表面積を有す
るゼオライトに担持させた触媒を用いることができる
が、特に脱アルミニウム処理したＹ型ゼオライトの細孔
内部に移動したアルミナナノ粒子に担持された、Ｆｅ−
Ｃｕ−Ｋ−Ａｌ系二酸化炭素還元触媒を用いるのが好ま
しい。Next, as the carbon dioxide reduction catalyst component,
Conventionally known iron-based carbon dioxide reduction catalysts, copper-based carbon dioxide reduction catalysts, and catalysts obtained by supporting these catalysts on zeolite having a high surface area can be used, but especially dealuminated Y-type zeolite Fe-supported by alumina nanoparticles that have moved inside the pores of
It is preferable to use a Cu-K-Al-based carbon dioxide reduction catalyst.
【００１５】このような二酸化炭素還元触媒成分は、例
えば、銅、鉄、カリウムの各水溶性塩を所定の割合で含
む水溶液に、所望に応じ脱アルミニウム処理したＹ型ゼ
オライトを加え、加熱反応させ、反応混合物を蒸発乾固
したのち粉砕し、酸素気流中３００〜５００℃で１〜３
時間焼成し、次いで水素気流中３００〜５００℃で１〜
３時間還元することにより調製される。この際の銅、
鉄、カリウムの混合比は、銅塩１モル当り、鉄塩２０〜
５０モル、カリウム塩１５〜３５モルの範囲内で選ばれ
る。また、脱アルミニウム処理したＹ型ゼオライト１０
０質量部に対する各金属の担持量としては、０．１〜１
０質量％の範囲が適当である。Such a carbon dioxide reduction catalyst component is prepared, for example, by adding dealuminated Y-type zeolite to an aqueous solution containing water-soluble salts of copper, iron and potassium in a predetermined ratio, and reacting with heating. The reaction mixture is evaporated to dryness and then crushed, and the mixture is crushed in an oxygen stream at 300 to 500 ° C.
Baking for 1 hour, then in a hydrogen stream at 300-500 ° C for 1-
Prepared by reducing for 3 hours. Copper at this time,
The mixing ratio of iron and potassium is 20-
It is selected within the range of 50 mol and 15 to 35 mol of potassium salt. Further, dealuminated Y-type zeolite 10
The supported amount of each metal with respect to 0 parts by mass is 0.1 to 1
A range of 0 mass% is suitable.
【００１６】本発明の二酸化炭素還元用複合光触媒は、
前記の半導体光触媒成分と二酸化炭素還元触媒成分とを
質量比１：５ないし５：１好ましくは１：２ないし２：
１の割合で混合し、粉砕後、１００〜８５０μｍの粒径
に造粒して所望の二酸化炭素還元用複合光触媒を製造す
ることができる。The composite photocatalyst for carbon dioxide reduction of the present invention comprises:
The mass ratio of the semiconductor photocatalyst component and the carbon dioxide reduction catalyst component is 1: 5 to 5: 1, preferably 1: 2 to 2:
The mixture can be mixed at a ratio of 1, pulverized, and then granulated to have a particle size of 100 to 850 μm to manufacture a desired composite photocatalyst for carbon dioxide reduction.
【００１７】次に添付図面に従って本発明方法を説明す
る。図１は、本発明方法を行うのに好適な反応装置の１
例を示す説明図であり、石英製太陽光受光セル１の底部
には吸収材料２例えば蒸留水を吸収させた石英ウールを
充填し、その上に本発明の二酸化炭素還元用複合光触媒
３が載置されている。そして、この複合光触媒３の内部
には温度センサー例えば熱電対４が配置され、これは冷
接点温度補償器５及びデータ収集装置６に接続し、この
データ収集装置６は、さらに温度看視装置７に信号を出
力している。Next, the method of the present invention will be described with reference to the accompanying drawings. FIG. 1 shows a reactor suitable for carrying out the method of the present invention.
FIG. 3 is an explanatory view showing an example, in which the bottom portion of the quartz solar light receiving cell 1 is filled with an absorbing material 2, for example, quartz wool which has absorbed distilled water, and the carbon dioxide reduction composite photocatalyst 3 of the present invention is mounted thereon. It is placed. A temperature sensor, for example, a thermocouple 4 is arranged inside the composite photocatalyst 3, which is connected to a cold junction temperature compensator 5 and a data collecting device 6, and the data collecting device 6 further includes a temperature monitoring device 7 Is outputting a signal to.
【００１８】また、図２は、この反応装置の太陽受光セ
ル１に太陽光を集光させるための集光型太陽光追尾光反
応機構の斜視図であり、太陽光８は凹面鏡９により集光
され、受光セル１に投射される。この受光セル１は、太
陽を自動的に追尾する赤道儀１０に取り付けられ、受光
セル１は常時太陽に対向して回転するようになってい
る。FIG. 2 is a perspective view of a concentrating sunlight tracking light reaction mechanism for concentrating sunlight on the solar light receiving cell 1 of this reaction apparatus. The sunlight 8 is condensed by the concave mirror 9. And is projected onto the light receiving cell 1. The light-receiving cell 1 is attached to an equatorial mount 10 that automatically tracks the sun, and the light-receiving cell 1 always rotates so as to face the sun.
【００１９】本発明方法に従えば、受光セル１中の吸水
材料２に蒸留水を吸収させ、５０〜３００ｋＰａの圧力
で二酸化炭素を導入し、受光セル１を太陽光の集光点に
位置するように赤道儀１０を設定し、受光セル１内で光
反応を行わせる。次いで生成した気体を取り出し、ガス
クロマトグラフィーによって検出し、また液体をマイク
ロシリンジを用いてガスクロマトグラフィに導入し、生
成物を検出した。このようにしてホルムアルデヒド、ギ
酸、メタン、メチルアルコール、エチルアルコールの生
成が認められた。この際の二酸化炭素の供給速度として
は、複合光触媒の質量に基づき１〜１００ｍｌ／分、好
ましくは５〜２０ｍｌ／分の範囲で選ばれる。According to the method of the present invention, the water absorbing material 2 in the light receiving cell 1 is made to absorb distilled water, carbon dioxide is introduced at a pressure of 50 to 300 kPa, and the light receiving cell 1 is positioned at the sunlight condensing point. The equatorial mount 10 is set so that the photoreaction is performed in the light receiving cell 1. The gas produced was then removed and detected by gas chromatography and the liquid was introduced into the gas chromatography using a microsyringe and the product was detected. In this way, formation of formaldehyde, formic acid, methane, methyl alcohol and ethyl alcohol was confirmed. The supply rate of carbon dioxide at this time is selected in the range of 1 to 100 ml / min, preferably 5 to 20 ml / min based on the mass of the composite photocatalyst.
【００２０】[0020]
【実施例】次に、実施例により本発明をさらに詳細に説
明するが、本発明は、これらの例によってなんら限定さ
れるものではない。EXAMPLES The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
【００２１】実施例１
硝酸カリウム０．０３３モルと、硝酸鉄（ＩＩＩ）九水
合物０．０４７モルと、硝酸銅（ＩＩ）三水合物０．０
０１４モルを、蒸留水３０ｍｌに加え、ガラス棒でよく
混合した。次に脱アルミニウム処理したＹ型ゼオライト
３０グラムをこれに加えて、かきまぜながら蒸発乾固し
た。得られた固形物を磁製乳鉢に移し、乳棒で微粉砕し
たのち、磁製ボートに入れ、酸素気流（流量＝３０ｍｌ
／分）中で、４００℃で２時間焼成したのち、さらに水
素気流（流量＝２０ｍｌ／分）で、４００℃で２時間還
元を行った。Example 1 0.033 mol of potassium nitrate, 0.047 mol of iron (III) nitrate nonahydrate and 0.03 mol of copper (II) nitrate trihydrate.
014 mol was added to 30 ml of distilled water and mixed well with a glass rod. Next, 30 g of dealuminated Y-type zeolite was added thereto, and the mixture was evaporated to dryness while stirring. The obtained solid is transferred to a porcelain mortar and finely pulverized with a pestle, and then placed in a porcelain boat, and an oxygen stream (flow rate = 30 ml).
/ Min), and then calcined at 400 ° C. for 2 hours, and then further reduced at 400 ° C. for 2 hours with a hydrogen stream (flow rate = 20 ml / min).
【００２２】別に炭酸カリウム０．０２０８モルと、二
酸化チタン０．１２５モルとを、蒸留水８０ｍｌに加
え、かきまぜながら蒸発乾固した。得られた固形物を１
１０℃で乾燥させたのち、空気中９４０℃で２０時間焼
成した。得られたＫ2Ｔｉ6Ｏ13粉末３．０グラムを、２
モル／リットル濃度の炭酸ナトリウム水溶液６０ｍｌと
１０００ｐｐｍ塩化白金酸水溶液９ｍｌに加え、よく分
散させたのち、水銀ランプ下１０時間照射して白金の担
持を行った。得られた白金担持Ｋ2Ｔｉ6Ｏ13を水で洗浄
し、１２０℃で１２時間乾燥させた。このようにして調
製した鉄系二酸化炭素還元触媒と白金担持Ｋ2Ｔｉ6Ｏ13
光触媒とを質量比１：１でよく混合したのち、１００〜
８５０μｍの大きさの粒子に造粒することにより、二酸
化炭素還元用光触媒を製造した。Separately, 0.0208 mol of potassium carbonate and 0.125 mol of titanium dioxide were added to 80 ml of distilled water and evaporated to dryness while stirring. 1 solid obtained
After drying at 10 ° C., it was baked in air at 940 ° C. for 20 hours. 3.0 g of the obtained K 2 Ti 6 O 13 powder was added to 2
After adding 60 ml of an aqueous solution of sodium carbonate having a concentration of mol / liter and 9 ml of an aqueous solution of 1000 ppm chloroplatinic acid to disperse well, irradiation with a mercury lamp was carried out for 10 hours to support platinum. The platinum-supported K 2 Ti 6 O 13 thus obtained was washed with water and dried at 120 ° C. for 12 hours. The iron-based carbon dioxide reduction catalyst thus prepared and platinum-supported K 2 Ti 6 O 13
After mixing well with the photocatalyst at a mass ratio of 1: 1, 100-
A photocatalyst for carbon dioxide reduction was manufactured by granulating into particles having a size of 850 μm.
【００２３】実施例２
石英製太陽光受光セルの底部に、石英ウール０．２８７
グラムを入れ、蒸留水２．０ｍｌを加えた。さらに、石
英ウール上部に、実施例１で得た複合化二酸化炭素固定
化触媒３．０グラムを入れ、蒸留水２．０ｍｌを加え
た。Ｐｔ−Ｐｔ／Ｒｈ１３％熱電対を触媒層の太陽光受
光面に配置し、受光セル内部を真空脱気したのち、二酸
化炭素を２×１０2ｋＰａの圧で導入し、平成１３年１
０月１２日午前９時３０分から午後４時３０分の間、太
陽光を反応セルに焦点照射した。この日、セル中の最高
反応温度は３２７℃であった。得られた受光セル内部の
生成物を表１に示す。Example 2 On the bottom of a quartz solar cell, quartz wool 0.287 was applied.
Grams were added and 2.0 ml of distilled water was added. Further, 3.0 g of the composite carbon dioxide-immobilized catalyst obtained in Example 1 was put on the upper part of the quartz wool, and 2.0 ml of distilled water was added. A Pt-Pt / Rh 13% thermocouple was placed on the solar light receiving surface of the catalyst layer, the interior of the light receiving cell was vacuum degassed, and then carbon dioxide was introduced at a pressure of 2 × 10 2 kPa.
Sunlight was focused on the reaction cell from 9:30 am to 4:30 pm on 12th October. On this day, the maximum reaction temperature in the cell was 327 ° C. The products inside the obtained light-receiving cell are shown in Table 1.
【００２４】実施例３
石英製太陽光受光セルの底部に、石英ウール０．１３５
グラムを入れ、蒸留水１．０ｍｌを加えた。さらに、石
英ウール上に、実施例１で製造した複合化二酸化炭素固
定化触媒０．１グラムを入れ、蒸留水１．０ｍｌを加え
た。次いで、受光セル内部を真空脱気したのち、二酸化
炭素を２×１０2ｋＰａの圧で導入し、平成１３年１１
月４日午前９時４６分から午後４時３５分の間、太陽光
を反応セルに焦点照射した。この日、セル中の最高反応
温度は３１４℃であった。得られた受光セル内部の生成
物を表１に示す。Example 3 0.135 quartz wool was added to the bottom of the quartz solar cell.
Grams were added and 1.0 ml of distilled water was added. Further, 0.1 g of the composite carbon dioxide-immobilized catalyst produced in Example 1 was put on quartz wool, and 1.0 ml of distilled water was added. Next, after degassing the inside of the light receiving cell in vacuum, carbon dioxide was introduced at a pressure of 2 × 10 2 kPa.
Sunlight was focused on the reaction cell from 9:46 am to 4:35 pm on the 4th of the month. On this day, the maximum reaction temperature in the cell was 314 ° C. The products inside the obtained light-receiving cell are shown in Table 1.
【００２５】実施例４
石英製太陽光受光セルの底部に、石英ウール０．３０１
グラムを入れ、蒸留水２．０ｍｌを加えた。石英ウール
上に、実施例１で製造した複合化二酸化炭素固定化触媒
３．０グラムを入れ、蒸留水を２．０ｍｌを加えた。受
光セル内部を真空脱気したのち、二酸化炭素を８５ｋＰ
ａ導入し、平成１３年１１月７日午前９時２８分から午
後４時１８分の間、太陽光を反応セルに焦点照射した。
この日、セル中の最高反応温度は２７８℃であった。受
光セル内の生成物を表１に示す。Example 4 On the bottom of a quartz solar cell, quartz wool 0.301 was added.
Grams were added and 2.0 ml of distilled water was added. 3.0 g of the composite carbon dioxide-immobilized catalyst produced in Example 1 was put on quartz wool, and 2.0 ml of distilled water was added. After degassing the inside of the light receiving cell in a vacuum, carbon dioxide is supplied at 85 kP
a was introduced and the reaction cell was focused and irradiated with sunlight from 9:28 am to 4:18 pm on November 7, 2001.
On this day, the maximum reaction temperature in the cell was 278 ° C. The products in the light receiving cell are shown in Table 1.
【００２６】実施例５
石英製太陽光受光セルの底部に、石英ウール０．２７３
グラムを入れ、０．１モル／リットル水酸化ナトリウム
１．０ｍｌを加えた。石英ウールに、実施例１で製造し
た複合化二酸化炭素固定化触媒３．０グラムを入れ、
０．１モル／リットル水酸化ナトリウム１．５ｍｌを加
えた。受光セル内部を真空脱気したのち、二酸化炭素を
９６ｋＰａの圧で導入し、平成１３年１１月２０日午前
１１時１０分から午後４時１８分の間、及び１１月２１
日午前９時２０分から午後２時３０分の間、太陽光を反
応セルに焦点照射した。この間、セル中の最高反応温度
は２６２℃であった。受光セル内の生成物を表１に示
す。Example 5 At the bottom of a solar cell made of quartz, 0.273 of quartz wool was used.
Gram was added and 1.0 ml of 0.1 mol / liter sodium hydroxide was added. Quartz wool was charged with 3.0 g of the composite carbon dioxide-immobilized catalyst produced in Example 1,
1.5 ml of 0.1 mol / liter sodium hydroxide was added. After degassing the inside of the light-receiving cell in vacuum, carbon dioxide was introduced at a pressure of 96 kPa, from 11:10 am to 4:18 pm on November 20, 2001, and November 21.
Sunlight was focused on the reaction cell from 9:20 am to 2:30 pm on the day. During this time, the maximum reaction temperature in the cell was 262 ° C. The products in the light receiving cell are shown in Table 1.
【００２７】実施例６
石英製太陽光受光セルの底部に、石英ウール０．１０２
グラムを入れ、０．１モル／リットル水酸化ナトリウム
０．５ｍｌを加えた。石英ウール上に、実施例１で調製
した複合化二酸化炭素固定化光触媒１．０グラムを入
れ、０．１モル／リットル水酸化ナトリウム０．５ｍｌ
を加えた。受光セル内部を真空脱気した後、二酸化炭素
を９６ｋＰａの圧で導入し、平成１３年１２月３日午前
９時１３分から午後４時２８分の間、太陽光を反応セル
に焦点照射した。この間、セル中の最高反応温度は２５
８℃であった。受光セル内の生成物を表１に示す。Example 6 On the bottom of a quartz solar cell, quartz wool 0.102 was used.
Gram was added and 0.5 ml of 0.1 mol / liter sodium hydroxide was added. 1.0 g of the composite carbon dioxide-immobilized photocatalyst prepared in Example 1 was put on quartz wool, and 0.5 ml of 0.1 mol / liter sodium hydroxide was added.
Was added. After degassing the inside of the light-receiving cell in vacuum, carbon dioxide was introduced at a pressure of 96 kPa, and sunlight was focused on the reaction cell from 9:13 am to 4:28 pm on December 3, 2001. During this time, the maximum reaction temperature in the cell is 25
It was 8 ° C. The products in the light receiving cell are shown in Table 1.
【００２８】実施例７
石英製太陽光受光セルの底部に、石英ウール０．２４３
グラムを入れ、０．１モル／リットル水酸化ナトリウム
０．５ｍｌを加えた。石英ウール上に、実施例１で調製
した複合化二酸化炭素固定化光触媒１．０グラムを入
れ、０．１モル／リットル水酸化ナトリウム０．５ｍｌ
を再び加えた。受光セル内部を真空脱気したのち、二酸
化炭素を２．０×１０2Ｐａ導入し、平成１３年１２月
６日午前９時３０分から午後２時３８分の間、及び１２
月７日午前９時３３分から午後１時４２分の間、太陽光
を反応セルに焦点照射した。この間、セル中の最高反応
温度は２５１℃であった。受光セル内の生成物を表１に
示す。Example 7 On the bottom of a quartz solar cell, 0.243 quartz wool was used.
Gram was added and 0.5 ml of 0.1 mol / liter sodium hydroxide was added. 1.0 g of the composite carbon dioxide-immobilized photocatalyst prepared in Example 1 was put on quartz wool, and 0.5 ml of 0.1 mol / liter sodium hydroxide was added.
Was added again. After degassing the inside of the light receiving cell in a vacuum, carbon dioxide was introduced at 2.0 × 10 2 Pa, and from 9:30 am to 2:38 pm on December 6, 2001, and 12
Sunlight was focused on the reaction cell from 9:33 am to 1:42 pm on the 7th of the month. During this time, the maximum reaction temperature in the cell was 251 ° C. The products in the light receiving cell are shown in Table 1.
【００２９】[0029]
【表１】 [Table 1]
【００３０】[0030]
【発明の効果】本発明によれば、太陽のエネルギーを利
用して、二酸化炭素の還元反応を高い効率で行わせるこ
とにより、ホルムアルデヒド、ギ酸、メタン、メチルア
ルコール、エチルアルコールなどの有用化合物を製造す
ることができる。INDUSTRIAL APPLICABILITY According to the present invention, useful compounds such as formaldehyde, formic acid, methane, methyl alcohol, and ethyl alcohol are produced by using the energy of the sun to carry out the reduction reaction of carbon dioxide with high efficiency. can do.
【図１】 本発明方法を行うのに好適な反応装置の１例
の説明図。FIG. 1 is an explanatory view of an example of a reaction apparatus suitable for carrying out the method of the present invention.
【図２】 図１の反応装置の集光型太陽光追尾反応機構
の斜視図。FIG. 2 is a perspective view of a concentrating solar tracking reaction mechanism of the reaction device of FIG.
１ 太陽光受光セル ２ 吸収材料 ３ 二酸化炭素還元用複合光触媒 ４ 熱電対 ５ 冷接点温度補償器 ６ データ収集装置 ７ 温度看視装置 1 solar light receiving cell 2 absorbing material 3 Composite photocatalyst for carbon dioxide reduction 4 thermocouple 5 Cold junction temperature compensator 6 Data collection device 7 Temperature monitoring device
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０７Ｃ 9/04 Ｃ０７Ｃ 9/04 27/00 27/00 31/04 31/04 31/08 31/08 47/04 47/04 53/02 53/02 // Ｃ０７Ｂ 61/00 ３００ Ｃ０７Ｂ 61/00 ３００ (72)発明者 官 国清 佐賀県鳥栖市宿町字野々下807番地１ 独 立行政法人産業技術総合研究所九州センタ ー内 (72)発明者 木田 徹也 佐賀県鳥栖市宿町字野々下807番地１ 独 立行政法人産業技術総合研究所九州センタ ー内 Ｆターム(参考） 4G069 AA02 AA08 BA07B BA48A BB06B BC03B BC31B BC66B BC75B CB62 CB70 CB74 EA02Y 4H006 AA02 AC11 AC41 AC45 AC46 BA02 BA05 BA09 BA10 BA19 BA30 BA71 BA95 BE41 BE60 FE11 4H039 CA60 CA62 CA65 CB20 CL00─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI theme code (reference) C07C 9/04 C07C 9/04 27/00 27/00 31/04 31/04 31/08 31/08 47 / 04 47/04 53/02 53/02 // C07B 61/00 300 C07B 61/00 300 (72) Inventor Kokusei 807 Nonoshita, No. 1 in the town of Tosu City, Tosu City, Saga Prefecture 1 In the Kyushu Center (72) Inventor Tetsuya Kida 807 Nonoshita, Tojuku-cho, Tosu City, Saga 1 F-Term (Reference) 4K069 AA02 AA08 BA07B BA48A BB06B BC03B BC31B BC66B BC75B CB62 CB70 CB74 EA02Y 4H006 AA02 AC11 AC41 AC45 AC46 BA02 BA05 BA09 BA10 BA19 BA30 BA71 BA95 BE41 BE60 FE11 4H039 CA60 CA62 CA65 CB20 CL00
Claims (8)
成分との複合化物から成る二酸化炭素還元用複合光触
媒。1. A composite photocatalyst for carbon dioxide reduction comprising a composite of a semiconductor photocatalyst component and a carbon dioxide reduction catalyst component.
成分との含有割合が１：５ないし５：１の範囲内にある
請求項１記載の二酸化炭素還元用複合光触媒。2. The composite photocatalyst for carbon dioxide reduction according to claim 1, wherein the content ratio of the semiconductor photocatalyst component and the carbon dioxide reduction catalyst component is in the range of 1: 5 to 5: 1.
したチタン系複合酸化物である請求項１又は２記載の二
酸化炭素還元用複合光触媒。3. The composite photocatalyst for reducing carbon dioxide according to claim 1, wherein the semiconductor photocatalyst component is a titanium-based composite oxide carrying a noble metal promoter.
−Ｋ−Ａｌ系触媒である請求項１、２又は３記載の二酸
化炭素還元用複合光触媒。4. The carbon dioxide reduction catalyst component is Fe--Cu.
The composite photocatalyst for carbon dioxide reduction according to claim 1, 2 or 3, which is a -K-Al based catalyst.
トに担持されている請求項４記載の二酸化炭素還元用複
合光触媒。5. The composite photocatalyst for carbon dioxide reduction according to claim 4, wherein the Fe—Cu—K—Al catalyst is supported on zeolite.
13であり、二酸化炭素還元触媒成分がゼオライトに担持
されたＦｅ−Ｃｕ−Ｋ−Ａｌ系触媒である請求項１ない
し５のいずれかに記載の二酸化炭素還元用複合光触媒。6. The semiconductor photocatalyst component is platinum-supported K 2 Ti 6 O.
13. The composite photocatalyst for carbon dioxide reduction according to claim 1, wherein the carbon dioxide reduction catalyst component is 13 and is a Fe—Cu—K—Al-based catalyst supported on zeolite.
酸化炭素還元用複合光触媒の存在下で、水と二酸化炭素
の混合物に太陽光を照射し、ホルムアルデヒド、ギ酸、
メタン、メチルアルコール及びエチルアルコールの中か
ら選ばれる少なくとも１種の化合物を生成させることを
特徴とする二酸化炭素光還元方法。7. A mixture of water and carbon dioxide is irradiated with sunlight in the presence of the composite photocatalyst for reducing carbon dioxide according to claim 1 to formaldehyde, formic acid,
A carbon dioxide photoreduction method characterized by producing at least one compound selected from methane, methyl alcohol and ethyl alcohol.
う請求項７記載の二酸化炭素光還元方法。8. The carbon dioxide photoreduction method according to claim 7, which is carried out by using a concentrating solar tracking photoreaction mechanism.
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