JPH10244163A - Photocatalyst having catalytic activity in visible light range - Google Patents
Photocatalyst having catalytic activity in visible light rangeInfo
- Publication number
- JPH10244163A JPH10244163A JP9049014A JP4901497A JPH10244163A JP H10244163 A JPH10244163 A JP H10244163A JP 9049014 A JP9049014 A JP 9049014A JP 4901497 A JP4901497 A JP 4901497A JP H10244163 A JPH10244163 A JP H10244163A
- Authority
- JP
- Japan
- Prior art keywords
- photocatalyst
- visible light
- hydrogen
- oxygen
- water
- 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.)
- Pending
Links
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 10
- 239000011941 photocatalyst Substances 0.000 title claims description 28
- 239000001257 hydrogen Substances 0.000 claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000001301 oxygen Substances 0.000 claims abstract description 19
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 19
- 239000010949 copper Substances 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims 1
- 238000000354 decomposition reaction Methods 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 3
- 239000012298 atmosphere Substances 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract 2
- 229910018274 Cu2 O Inorganic materials 0.000 abstract 2
- 229910016514 CuFeO2 Inorganic materials 0.000 abstract 2
- 229910017344 Fe2 O3 Inorganic materials 0.000 abstract 1
- 239000000470 constituent Substances 0.000 abstract 1
- 229910052757 nitrogen Inorganic materials 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- 229910052815 sulfur oxide Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- -1 silver ions Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material Substances 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
- 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
-
- 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
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Landscapes
- Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、光で水を分解し、
水素と酸素の双方を同時に生成させる酸化物から成る光
触媒に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention
The present invention relates to a photocatalyst comprising an oxide which simultaneously produces both hydrogen and oxygen.
【０００２】[0002]
【従来の技術】現在、エネルギー源としては様々なもの
が用いられている。産業革命以後大量に使われ始めた石
油や石炭等の化石燃料は、その埋蔵量は無限ではなく、
燃焼させた際に二酸化炭素、窒素酸化物、硫黄酸化物等
が排出される。その結果、二酸化炭素は地球の温暖化を
もたらし、窒素酸化物や硫黄酸化物は酸性雨の原因とな
って環境破壊をもたらしている。又、新しいエネルギー
源として原子力発電が実用化されているが、安全性や廃
棄物処理等の問題を抱えている。このような状況の下
で、エネルギー資源や地球環境の問題を解決する一方法
としてクリーンなエネルギー源の一つである水素が注目
されている。水素は燃焼させても水になるのみであり、
環境汚染を引き起こさない。しかし、水素を発生させる
ために化石燃料等を用いたのでは意味がなくなってしま
う。光エネルギーから水素といった化学エネルギーを取
り出す方法の一つに、光照射によって水を水素、酸素に
分解する無機酸化物半導体粒子を用いた光触媒がある。
光触媒は、そのバンドギャップ以上のエネルギーを吸収
すると、ホールとエレクトロンを生成し、これらがそれ
ぞれ酸化反応、還元反応を行い、酸素、水素を発生させ
る。この光触媒の実用化を考えた場合、光源として太陽
光の利用は不可欠である。地表に降り注ぐ太陽光は、可
視光である波長500nm 付近に放射の最大強度をもってお
り、波長 400〜750nm の可視光領域のエネルギー量は全
太陽光の約43％である。一方、波長 400nm以下の紫外線
領域では５％にも満たない。従って、太陽光スペクトル
を効率よく利用するためには、可視光の光にも触媒活性
をもつ光触媒が望まれている。2. Description of the Related Art At present, various energy sources are used. Fossil fuels such as oil and coal that have begun to be used in large quantities since the Industrial Revolution have infinite reserves,
When burned, carbon dioxide, nitrogen oxides, sulfur oxides and the like are emitted. As a result, carbon dioxide causes global warming, and nitrogen oxides and sulfur oxides cause acid rain and cause environmental destruction. Further, nuclear power generation has been put into practical use as a new energy source, but has problems such as safety and waste disposal. Under such circumstances, attention has been paid to hydrogen, which is one of the clean energy sources, as a method for solving the problems of energy resources and the global environment. Hydrogen is only turned into water when burned,
Does not cause environmental pollution. However, the use of fossil fuel or the like to generate hydrogen is meaningless. One of the methods for extracting chemical energy such as hydrogen from light energy is a photocatalyst using inorganic oxide semiconductor particles that decompose water into hydrogen and oxygen by light irradiation.
When the photocatalyst absorbs energy equal to or greater than its band gap, it generates holes and electrons, which respectively perform an oxidation reaction and a reduction reaction to generate oxygen and hydrogen. When considering the practical use of this photocatalyst, utilization of sunlight as a light source is indispensable. The sunlight falling on the surface of the earth has the maximum intensity of radiation near the visible wavelength of 500 nm, and the energy content in the visible light range from 400 to 750 nm is about 43% of the total sunlight. On the other hand, it is less than 5% in the ultraviolet region having a wavelength of 400 nm or less. Therefore, in order to use the solar spectrum efficiently, a photocatalyst having catalytic activity even for visible light is desired.
【０００３】従来、可視光領域で比較的高い触媒活性を
示す光触媒として、特開平 8-89804に開示されたものが
ある。これは、複合酸化物を構成する元素として、可視
光領域に吸収をもつ遷移金属元素を用いたものである。
又、紫外光を照射して水を分解し、水素と酸素の双方を
同時に生成させる光触媒としては、Ｎi を担持させたＫ
4Ｎb6Ｏ17が知られている。Conventionally, a photocatalyst exhibiting relatively high catalytic activity in the visible light region is disclosed in Japanese Patent Application Laid-Open No. 8-89804. This uses a transition metal element having absorption in a visible light region as an element constituting the composite oxide.
As a photocatalyst for irradiating ultraviolet light to decompose water and simultaneously generate both hydrogen and oxygen, Ni-supported K
4 Nb 6 O 17 is known.
【０００４】[0004]
【発明が解決しようとする課題】特開平 8-89804に記載
された光触媒は、可視光にも活性をもち、メタノール水
溶液の分解反応において水素の発生が認められている
が、水の分解反応については記載されていない。今まで
見い出されてきた光触媒物質は、可視光が利用できても
活性が低く、しかも水分解反応において水素か酸素のい
ずれか一方しか発生させることができなかった。このよ
うに、水素、酸素のいずれか一方が発生しない場合、光
照射によって生成されたホールとエレクトロンがそれぞ
れ有効に反応に関与していないこととなり、触媒の寿命
が短くなったり、活性の値が低くなったりして触媒機能
の安定性に欠けることになる。The photocatalyst described in JP-A-8-89804 has activity in visible light, and generation of hydrogen has been observed in the decomposition reaction of an aqueous methanol solution. Is not listed. The photocatalytic substances found so far have low activity even when visible light can be used, and they can only generate either hydrogen or oxygen in the water splitting reaction. As described above, when either one of hydrogen and oxygen is not generated, holes and electrons generated by light irradiation do not effectively participate in the reaction, and the life of the catalyst is shortened or the activity value is reduced. The stability of the catalytic function is lost due to the decrease in the temperature.
【０００５】又、上述のＮi を担持させたＫ4Ｎb6Ｏ17
は、エネルギーの高い紫外光を照射したときに水素と酸
素の双方を生成させるに過ぎなかった。そこで本発明の
目的は、太陽光の利用効率が高く、長時間安定した触媒
機能を有する光触媒を提供することにある。Further, K 4 Nb 6 O 17 carrying Ni described above is used.
Merely produced both hydrogen and oxygen when irradiated with high energy ultraviolet light. Therefore, an object of the present invention is to provide a photocatalyst having high utilization efficiency of sunlight and having a stable catalytic function for a long time.
【０００６】[0006]
【課題を解決するための手段】本発明の請求項１に記載
の発明は、「可視光の照射により水を分解し、且つ水素
と酸素の双方を同時に生成させる、１価の銅を含む酸化
物から成る」光触媒である。According to the first aspect of the present invention, there is provided an oxide containing monovalent copper, which decomposes water by irradiation with visible light and simultaneously generates both hydrogen and oxygen. A photocatalyst.
【０００７】１価の銅を含む酸化物としては、Ｃu2Ｏが
好ましい（請求項２）。又、１価の銅を含む酸化物とし
ては、３価の元素Ｍを含む化学式ＣuＭＯ2 で表される
化合物が好ましい（請求項３）。The oxide containing monovalent copper is preferably Cu 2 O (claim 2). As the oxide containing monovalent copper, a compound represented by the chemical formula CuMO 2 containing a trivalent element M is preferable (claim 3).
【０００８】[0008]
【発明の実施の形態】本発明の光触媒は、１価の銅を含
む化合物であり、これを水中に入れ、可視光を照射する
と、水分解反応により水素と酸素の双方を同時に発生す
るものである。そのメカニズムは、光エネルギーによっ
て励起され生成したホールとエレクトロンがそれぞれ酸
化反応、還元反応を引き起こし、水に起因する酸素と水
素を同時に発生させるというものである。BEST MODE FOR CARRYING OUT THE INVENTION The photocatalyst of the present invention is a compound containing monovalent copper. When the photocatalyst is placed in water and irradiated with visible light, both hydrogen and oxygen are simultaneously generated by a water decomposition reaction. is there. The mechanism is that holes and electrons generated by excitation by light energy cause an oxidation reaction and a reduction reaction, respectively, and simultaneously generate oxygen and hydrogen due to water.
【０００９】本発明の請求項第２項に記載したＣu2Ｏ
は、最も単純な化合物であり、天然にも存在する。この
酸化銅の粉末を水の中に分散させ、光を照射するだけで
酸素及び水素が発生してくる。本発明の請求項第３項及
び４項に記載したＣuＭＯ2 は、一般式ＡＢＯ2 で表さ
れるデラフォサイト（Delafossite)型の結晶構造をもつ
物質である。元素Ｍは、３価の価数をもち、Ｃr,Ｍn,Ｆ
e,Ｃo,Ｇa からなる群から選択される。The Cu 2 O according to claim 2 of the present invention.
Is the simplest compound and also exists in nature. Oxygen and hydrogen are generated simply by dispersing the copper oxide powder in water and irradiating light. CuMO 2 described in claims 3 and 4 of the present invention is a substance having a delafossite crystal structure represented by the general formula ABO 2 . The element M has a trivalent valence, and Cr, Mn, F
It is selected from the group consisting of e, Co, and Ga.
【００１０】本発明の光触媒は、通常の固相法、すなわ
ち原料となる各金属成分の酸化物を目的組成の比率で混
合し、不活性ガス雰囲気下で焼成することで合成でき
る。本発明の光触媒の形状は、光を有効に利用するため
に表面積の大きい粒子であることが望ましく、一般には
粒子の大きさは 0.1〜10μm 、好ましくは 0.1〜 1μm
が適当である。このような粒径を得る慣用的な手段に
は、例えば、ボールミルや遊星ミルによる粉砕がある。
更に、本発明の光触媒に対しても、助触媒であるＰt や
Ｎi Ｏの担持等の光触媒製造に通常用いられるような修
飾を行うことができる。又、水分解反応を行う際に用い
る水は、純水に限らず、通常、水の分解反応によく用い
られるように、炭酸塩や炭酸水素塩等の塩類を混ぜた水
を用いてもよい。或いは、アルコールや銀イオン等の犠
牲試薬を用いて、水素、酸素のいずれか一方を生成させ
てもよい。以下、本発明を具体的に説明するが、本発明
はこれに限られたものではない。The photocatalyst of the present invention can be synthesized by a usual solid phase method, that is, by mixing oxides of respective metal components as raw materials at a ratio of a desired composition and firing the mixture under an inert gas atmosphere. The shape of the photocatalyst of the present invention is desirably particles having a large surface area in order to effectively utilize light, and the particle size is generally 0.1 to 10 μm, preferably 0.1 to 1 μm.
Is appropriate. Conventional means for obtaining such a particle size include, for example, grinding with a ball mill or a planetary mill.
Further, the photocatalyst of the present invention can be modified as commonly used for photocatalyst production, such as supporting Pt or NiO as a cocatalyst. Further, the water used for performing the water splitting reaction is not limited to pure water, and water containing a mixture of salts such as carbonates and bicarbonates may be used, as is commonly used for the water splitting reaction. . Alternatively, one of hydrogen and oxygen may be generated using a sacrificial reagent such as alcohol or silver ions. Hereinafter, the present invention will be specifically described, but the present invention is not limited thereto.
【００１１】（光触媒の製造方法１）本発明の化学式Ｃ
uＭＯ2 において、元素ＭとしてＦe を用い、Ｃu Ｆe
Ｏ2を合成した。合成は、各成分の酸化物を化学量論比
で調合し、固相法により行った。すなわち、Ｃu2Ｏを2.
36ｇ、Ｆe2Ｏ3 を2.64ｇそれぞれ秤量し、アルミナボー
トに入れて、窒素雰囲気の環状炉中で1050℃、10時間の
焼成を行った。焼成終了後、この焼成物を乳鉢で10μm
以下の大きさに粉砕した。得られた粉末状試料を粉末Ｘ
線回折により同定したところ、目的とするデラフォサイ
ト構造をもつ化合物が得られた。(Method 1 for producing photocatalyst) Chemical formula C of the present invention
In uMO 2 , Fe is used as the element M and CuFe
O 2 was synthesized. The synthesis was carried out by preparing the oxides of the respective components at a stoichiometric ratio and by a solid phase method. That is, Cu 2 O is converted to 2.
36 g and 2.64 g of Fe 2 O 3 were weighed, placed in an alumina boat, and fired at 1050 ° C. for 10 hours in an annular furnace in a nitrogen atmosphere. After firing, the fired product is 10 μm in a mortar
It was crushed to the following size. The obtained powdery sample is powder X
As a result of identification by line diffraction, a compound having an intended delafossite structure was obtained.
【００１２】（光触媒の製造方法２）本発明の化学式Ｃ
uＭＯ2 において、元素ＭとしてＧa を用い、Ｃu Ｇa
Ｏ2を合成した。合成は、各成分の酸化物を化学量論比
で調合し、固相法により行った。すなわち、Ｃu2Ｏを2.
16ｇ、Ｇa2Ｏ3 を2.84ｇそれぞれ秤量し、アルミナボー
トに入れて、窒素雰囲気の環状炉中で1050℃、10時間の
焼成を行った。焼成終了後、この焼成物を乳鉢で10μm
以下の大きさに粉砕した。得られた粉末状試料を粉末Ｘ
線回折により同定したところ、目的とするデラフォサイ
ト構造をもつ化合物が得られた。(Method 2 for producing photocatalyst) Chemical formula C of the present invention
In uMO 2 , Ga is used as the element M and Cu Ga
O 2 was synthesized. The synthesis was carried out by preparing the oxides of the respective components at a stoichiometric ratio and by a solid phase method. That is, Cu 2 O is converted to 2.
16 g and 2.84 g of Ga 2 O 3 were respectively weighed, placed in an alumina boat, and fired at 1050 ° C. for 10 hours in a ring furnace in a nitrogen atmosphere. After firing, the fired product is 10 μm in a mortar
It was crushed to the following size. The obtained powdery sample is powder X
As a result of identification by line diffraction, a compound having an intended delafossite structure was obtained.
【００１３】（触媒活性の評価）水分解用の光触媒の触
媒活性の評価は、上記製造方法１及び２で作製したＣu
Ｆe Ｏ2 、Ｃu Ｇa Ｏ2 と市販のＣu2Ｏについて行っ
た。水分解反応には、閉鎖循環系触媒反応装置を用い、
純水中に光触媒0.5gを入れ、マグネチックスターラーで
攪拌しながら外部から可視光を照射した。光源には 500
Ｗキセノンランプを用い、反応管としてはパイレックス
ガラス製のものを用いた。光源からの光は、短波長側の
光をカットするカットオフフィルターを透過させてか
ら、試料（光触媒）に照射した。(Evaluation of catalytic activity) The catalytic activity of the photocatalyst for water splitting was evaluated by using Cu prepared by the above-mentioned production methods 1 and 2.
It was performed on Fe O 2, Cu Ga O 2 with commercial Cu 2 O. For the water splitting reaction, a closed-circulation catalytic reactor was used,
0.5 g of a photocatalyst was put in pure water, and visible light was irradiated from the outside while stirring with a magnetic stirrer. 500 for light source
A W xenon lamp was used, and a reaction tube made of Pyrex glass was used. The light from the light source was transmitted through a cutoff filter that cuts light on the short wavelength side, and then irradiated onto the sample (photocatalyst).
【００１４】Ｃu Ｆe Ｏ2 、Ｃu Ｇa Ｏ2 については42
0nm 以下の波長の光をカットし、Ｃu2Ｏについては460n
m 以下の波長の光をカットし、照射を行った。尚、Ｃu2
Ｏは市販のもの２種類（和光純薬製及び関東化学製）を
用いた。生成した水素及び酸素の検出及び定量はガスク
ロマトグラフィーで行った。検出の結果、水素、酸素と
もに発生が認められ、その測定結果は表１のとおりであ
った。表１には、気体の生成活性を１時間当たりの生成
量で表示してある。[0014] Cu Fe O 2, for Cu Ga O 2 42
It cuts light with a wavelength of 0 nm or less and 460n for Cu 2 O.
The light having a wavelength of less than m was cut and irradiated. In addition, Cu 2
As O, two kinds of commercially available products (manufactured by Wako Pure Chemical Industries and manufactured by Kanto Chemical Co., Ltd.) were used. The detection and quantification of the generated hydrogen and oxygen were performed by gas chromatography. As a result of the detection, generation of both hydrogen and oxygen was recognized, and the measurement results were as shown in Table 1. Table 1 shows the gas generation activity in terms of the amount generated per hour.
【００１５】[0015]
【表１】 [Table 1]
【００１６】尚、本発明の光触媒は、水の分解反応だけ
ではなく、他の化学反応、例えば、有機物の分解反応や
貴金属イオンの還元反応にも適用することができる。The photocatalyst of the present invention can be applied not only to the decomposition reaction of water but also to other chemical reactions such as decomposition reaction of organic substances and reduction reaction of noble metal ions.
【００１７】[0017]
【発明の効果】以上の通り、本発明の１価の銅を含む化
合物からなる光触媒は、可視光の下で光触媒活性を示す
のみならず、水素と酸素の両方を同時に生成する。従っ
て、太陽光エネルギーの約43％を占める可視光を触媒反
応に利用でき、利用効率が大幅に上昇する。又、水素と
酸素の両方を同時に生成するので、触媒の寿命が長く保
つことができ、触媒機能の安定化に寄与する。As described above, the photocatalyst comprising the compound containing monovalent copper of the present invention not only exhibits photocatalytic activity under visible light, but also simultaneously generates both hydrogen and oxygen. Therefore, visible light which accounts for about 43% of the solar energy can be used for the catalytic reaction, and the use efficiency is greatly increased. In addition, since both hydrogen and oxygen are produced simultaneously, the life of the catalyst can be kept long, which contributes to stabilization of the catalyst function.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ０１Ｇ 3/00 Ｂ０１Ｊ 23/82 Ｍ 3/02 23/84 ３１１Ｍ (72)発明者 原 亨和 神奈川県横浜市緑区長津田町4259 東京工 業大学資源化学研究所内 (72)発明者 川副 博司 神奈川県横浜市緑区長津田町4259 東京工 業大学応用セラミックス研究所内 (72)発明者 細野 秀雄 神奈川県横浜市緑区長津田町4259 東京工 業大学応用セラミックス研究所内──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. 6 Identification code FI C01G 3/00 B01J 23/82 M 3/02 23/84 311M (72) Inventor Towakazu Hara Nagatsuda-cho, Midori-ku, Yokohama-shi, Kanagawa 4259 Inside the Institute of Natural Resources and Chemicals, Tokyo Institute of Technology (72) Inventor Hiroshi Kawasoe 4259 Nagatsuda-cho, Midori-ku, Yokohama-shi, Kanagawa Prefecture Inside the Institute of Applied Ceramics, Tokyo Institute of Technology (72) Hideo Hosono 4259, Tokyo Institute of Applied Ceramics, Institute of Technology
Claims (4)
素と酸素の双方を同時に生成させる、１価の銅を含む酸
化物から成ることを特徴とする、可視光領域で触媒活性
をもつ光触媒。1. A catalyst having a catalytic activity in the visible light region, comprising an oxide containing monovalent copper, which decomposes water by irradiation with visible light and simultaneously generates both hydrogen and oxygen. photocatalyst.
とを特徴とする請求項１に記載の光触媒。2. The photocatalyst according to claim 1, wherein the oxide is represented by a chemical formula Cu 2 O.
れ、前記Ｍは、３価の元素から選択された１種以上の元
素であることを特徴とする請求項１に記載の光触媒。3. The photocatalyst according to claim 1, wherein the oxide is represented by a chemical formula CuMO 2 , and the M is at least one element selected from trivalent elements.
る群から選択された１種以上の元素であることを特徴と
する請求項３に記載の光触媒。4. The photocatalyst according to claim 3, wherein said M is at least one element selected from the group consisting of Cr, Mn, Fe, Co, and Ga.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9049014A JPH10244163A (en) | 1997-03-04 | 1997-03-04 | Photocatalyst having catalytic activity in visible light range |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9049014A JPH10244163A (en) | 1997-03-04 | 1997-03-04 | Photocatalyst having catalytic activity in visible light range |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10244163A true JPH10244163A (en) | 1998-09-14 |
Family
ID=12819294
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9049014A Pending JPH10244163A (en) | 1997-03-04 | 1997-03-04 | Photocatalyst having catalytic activity in visible light range |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10244163A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008156130A (en) * | 2006-12-20 | 2008-07-10 | Mitsui Mining & Smelting Co Ltd | Delafossite type oxide, method for manufacturing the same and exhaust gas purification catalyst |
| JP2010207769A (en) * | 2009-03-12 | 2010-09-24 | Aomori Prefectural Industrial Technology Research Center | Photocatalyst for making hydrogen |
| CN106268813A (en) * | 2016-09-20 | 2017-01-04 | 天津城建大学 | A kind of CuFeO for photoelectrocatalysis2the preparation method of nano material |
-
1997
- 1997-03-04 JP JP9049014A patent/JPH10244163A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008156130A (en) * | 2006-12-20 | 2008-07-10 | Mitsui Mining & Smelting Co Ltd | Delafossite type oxide, method for manufacturing the same and exhaust gas purification catalyst |
| JP2010207769A (en) * | 2009-03-12 | 2010-09-24 | Aomori Prefectural Industrial Technology Research Center | Photocatalyst for making hydrogen |
| CN106268813A (en) * | 2016-09-20 | 2017-01-04 | 天津城建大学 | A kind of CuFeO for photoelectrocatalysis2the preparation method of nano material |
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