JP2008155099A - Photocatalyst for decomposing water and organic matter, and manufacturing method of this photocatalyst - Google Patents
Photocatalyst for decomposing water and organic matter, and manufacturing method of this photocatalyst Download PDFInfo
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- JP2008155099A JP2008155099A JP2006345205A JP2006345205A JP2008155099A JP 2008155099 A JP2008155099 A JP 2008155099A JP 2006345205 A JP2006345205 A JP 2006345205A JP 2006345205 A JP2006345205 A JP 2006345205A JP 2008155099 A JP2008155099 A JP 2008155099A
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 70
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000005416 organic matter Substances 0.000 title claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 63
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 63
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims abstract description 20
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 19
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims abstract description 19
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 15
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 14
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 14
- 239000011575 calcium Substances 0.000 claims abstract description 13
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 11
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 11
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 4
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 29
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 24
- 239000001301 oxygen Substances 0.000 abstract description 24
- 229910052760 oxygen Inorganic materials 0.000 abstract description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 23
- 239000001257 hydrogen Substances 0.000 abstract description 23
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 23
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- 231100000053 low toxicity Toxicity 0.000 abstract description 7
- 230000029553 photosynthesis Effects 0.000 abstract description 4
- 238000010672 photosynthesis Methods 0.000 abstract description 4
- 239000004480 active ingredient Substances 0.000 abstract description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 230000001699 photocatalysis Effects 0.000 description 7
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 6
- 229910052684 Cerium Inorganic materials 0.000 description 6
- 229960000907 methylthioninium chloride Drugs 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 5
- 230000001678 irradiating effect Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229910052707 ruthenium Inorganic materials 0.000 description 5
- 150000001785 cerium compounds Chemical class 0.000 description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000000295 emission spectrum Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 229910052691 Erbium Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000370 acceptor Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000006303 photolysis reaction Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910000018 strontium carbonate Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- MFEVGQHCNVXMER-UHFFFAOYSA-L 1,3,2$l^{2}-dioxaplumbetan-4-one Chemical compound [Pb+2].[O-]C([O-])=O MFEVGQHCNVXMER-UHFFFAOYSA-L 0.000 description 1
- 229910000003 Lead carbonate Inorganic materials 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000007059 acute toxicity Effects 0.000 description 1
- 231100000403 acute toxicity Toxicity 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- SEKOGOCBEZIJIW-UHFFFAOYSA-H antimony(3+);tricarbonate Chemical compound [Sb+3].[Sb+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O SEKOGOCBEZIJIW-UHFFFAOYSA-H 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- NQZFAUXPNWSLBI-UHFFFAOYSA-N carbon monoxide;ruthenium Chemical group [Ru].[Ru].[Ru].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] NQZFAUXPNWSLBI-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- VSQYNPJPULBZKU-UHFFFAOYSA-N mercury xenon Chemical compound [Xe].[Hg] VSQYNPJPULBZKU-UHFFFAOYSA-N 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical class [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- SJLOMQIUPFZJAN-UHFFFAOYSA-N oxorhodium Chemical compound [Rh]=O SJLOMQIUPFZJAN-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000002256 photodeposition Methods 0.000 description 1
- 231100000760 phototoxic Toxicity 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 229910003450 rhodium oxide Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 1
- 230000037072 sun protection Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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Abstract
Description
本発明は、水及び有機物の分解に用いられる光触媒、並びに該光触媒の製造方法に関する。 The present invention relates to a photocatalyst used for the decomposition of water and organic substances, and a method for producing the photocatalyst.
光エネルギーを利用して物質変換を行う方法として、光触媒の利用が挙げられる。光触媒については、光照射によって生じる電子で反応物を還元、正孔で反応物を酸化する能力を持つことが既に知られている。この技術を応用した有害物質の分解除去、部分酸化反応、および水分解反応などの化学反応プロセスは、環境およびエネルギー問題の観点から重要な課題になっている。光触媒には、光照射によって効率良く化学反応を進行させることはもとより、環境維持の観点から光触媒自身が毒性の低い材料から構成されることが要求される。これまでに開示されている光触媒の中では酸化チタンが高い光触媒活性を持ち、毒性の低い材料として知られている。 As a method for performing substance conversion using light energy, use of a photocatalyst can be mentioned. As for the photocatalyst, it is already known that it has the ability to reduce the reactant with electrons generated by light irradiation and oxidize the reactant with holes. Chemical reaction processes such as decomposition and removal of harmful substances, partial oxidation reaction, and water decomposition reaction to which this technology is applied have become important issues from the viewpoint of environmental and energy problems. The photocatalyst is required to be composed of a material having low toxicity from the viewpoint of maintaining the environment as well as allowing a chemical reaction to proceed efficiently by light irradiation. Among the photocatalysts disclosed so far, titanium oxide has a high photocatalytic activity and is known as a material having low toxicity.
一方、酸化セリウムは高い紫外線遮断能を持ち、紫外線吸収サングラス、自動車用紫外線カットガラス、日焼け防止化粧品などに幅広く応用されている。また、酸化セリウムは希土類の一種で極めて毒性が低く、人体に対して中毒性や急性毒性がない化合物として知られている。酸化セリウムは、その電子構造から光照射によって生成した電子とホールは直ちに再結合し、微弱な熱が放出される。したがって、酸化セリウムを光触媒として応用するには、光を吸収して生成した電子とホールを再結合させることなく反応物に接触させる必要がある。 On the other hand, cerium oxide has a high UV blocking ability and is widely applied to UV absorbing sunglasses, UV cut glass for automobiles, sun protection cosmetics and the like. Further, cerium oxide is a kind of rare earth and has extremely low toxicity, and is known as a compound having no toxicity or acute toxicity to the human body. In cerium oxide, electrons and holes generated by light irradiation from the electronic structure immediately recombine, and weak heat is released. Therefore, in order to apply cerium oxide as a photocatalyst, it is necessary to contact the reactants without recombining electrons and holes generated by absorbing light.
酸化セリウムは、その高い紫外線吸収能および低毒性から光触媒への応用が試みられている。（例えば、非特許文献１、２及び特許文献１、２参照）
上記の非特許文献1において、荒川らは酸化セリウム光触媒による水からの酸素生成について言及している。この場合、光照射により酸素を発生させるには、電子受容体として働くＦｅ３＋やＣｅ４＋が光触媒懸濁液中に存在することが必要である。電子受容体であるＦｅ３＋やＣｅ４＋が存在しない場合の、酸化セリウム光触媒による水素生成については言及していない。
In the above
非特許文献2には、 酸化チタンと少量の酸化セリウムを複合化することにより、有機物の光分解が促進されることが開示されている。同文献には、酸化セリウム単独の光触媒機能についての記述はない。また、水分解反応に対する活性については言及していない。 Non-Patent Document 2 discloses that photodecomposition of organic substances is promoted by combining titanium oxide and a small amount of cerium oxide. This document does not describe the photocatalytic function of cerium oxide alone. Moreover, it does not mention the activity with respect to the water splitting reaction.
特許文献１には、酸化チタン、酸化ジルコニウム、酸化セリウムのいずれか、あるいは複数を含有している光触媒のＮＯｘガスの浄化作用について開示されている。
また、特許文献２には、光触媒活性を有する粉末を酸化セリウムで被覆した複合化粉末を含む組成物が、医薬品、医薬部外品、化粧品等の外用組成物への応用に対して光毒性（光照射によって生成する電子とホールに由来する人体への悪影響）を抑制する能力を持つことが開示されている。
Patent Document 2 discloses that a composition containing a composite powder obtained by coating a powder having photocatalytic activity with cerium oxide is phototoxic for application to external compositions such as pharmaceuticals, quasi drugs, and cosmetics ( It has been disclosed that it has the ability to suppress adverse effects on the human body derived from electrons and holes generated by light irradiation.
これまでに酸化セリウムの光触媒機能に関する研究は多数あるが、水を水素と酸素に完全分解できるような高い光触媒機能を発現するものは知られていない。
したがって、本発明は毒性が低く、水を水素と酸素に完全に分解することができる光触媒、或いは高い活性を有する有機物分解用光触媒、及び光合成反応の光触媒等として有用な酸化セリウムを活性成分として含有する光触媒を提供することを目的とする。
There have been many studies on the photocatalytic function of cerium oxide so far, but no one that exhibits such a high photocatalytic function that can completely decompose water into hydrogen and oxygen has not been known.
Therefore, the present invention contains cerium oxide as an active ingredient which is low in toxicity and can be completely decomposed into hydrogen and oxygen, or a photocatalyst for decomposing organic matter having high activity, and a photocatalyst for a photosynthesis reaction. It aims at providing the photocatalyst which does.
本発明では、上記課題を解決するために、次の構成１〜６を採用する。
１．（１）酸化セリウムに、（２）カルシウム、ストロンチウム、イットリウム、ランタンからなる群から選択された異種元素を添加し、さらに（３）助触媒として酸化ルテニウム又は白金を担持したことを特徴とする水及び有機物分解用光触媒。
２．（２）異種元素の添加量が（１）酸化セリウムを基準として０．１〜５０モル％であり、（３）助触媒の担持量が（１）酸化セリウム及び（２）異種元素からなる複合体を基準として０．１〜１０重量％であることを特徴とする１に記載の光触媒。
３．前記光触媒が、（３）助触媒として酸化ルテニウムを担持した、水分解用光触媒であることを特徴とする１又は２に記載の光触媒。
４．前記光触媒が、（３）助触媒として白金を担持した、有機物分解用光触媒であることを特徴とする１又は２に記載の光触媒。
５．（１）酸化セリウムと、（２）カルシウム、ストロンチウム、イットリウム、又はランタンを含む化合物を混合し、得られた前駆体を空気中で５００〜１４００℃の温度に加熱した後に、（３）助触媒として酸化ルテニウム又は白金を担持することを特徴とする１〜４のいずれかに記載の光触媒の製造方法。
６．（１）硝酸セリウム又は塩化セリウムと、（２）カルシウム、ストロンチウム、イットリウム、又はランタンを含む化合物を水に溶解させ、ｐHを７以上に調整して得られた前駆体を空気中で５００〜１４００℃の温度に加熱した後に、（３）助触媒として酸化ルテニウム又は白金を担持することを特徴とする１〜４のいずれかに記載の光触媒の製造方法。
In this invention, in order to solve the said subject, the following structures 1-6 are employ | adopted.
1. (1) Water characterized by adding (2) a different element selected from the group consisting of calcium, strontium, yttrium, and lanthanum to cerium oxide, and (3) carrying ruthenium oxide or platinum as a promoter. And a photocatalyst for organic matter decomposition.
2. (2) The added amount of the different element is (1) 0.1 to 50 mol% based on cerium oxide, (3) the amount of the supported catalyst is (1) cerium oxide and (2) a composite comprising different elements 2. The photocatalyst according to 1, which is 0.1 to 10% by weight based on the body.
3. 3. The photocatalyst according to 1 or 2, wherein the photocatalyst is (3) a water splitting photocatalyst carrying ruthenium oxide as a cocatalyst.
4). 3. The photocatalyst according to 1 or 2, wherein the photocatalyst is (3) a photocatalyst for decomposing organic matter, wherein platinum is supported as a promoter.
5. (1) After mixing cerium oxide and (2) a compound containing calcium, strontium, yttrium, or lanthanum, and heating the resulting precursor to a temperature of 500-1400 ° C. in air, (3) promoter The method for producing a photocatalyst according to any one of 1 to 4, wherein ruthenium oxide or platinum is supported as
6). (1) A precursor obtained by dissolving a compound containing cerium nitrate or cerium chloride and (2) calcium, strontium, yttrium, or lanthanum in water and adjusting the pH to 7 or more in the air. (3) The method for producing a photocatalyst according to any one of 1 to 4, wherein ruthenium oxide or platinum is supported as a cocatalyst after heating to a temperature of ° C.
本発明で得られる光触媒は、毒性が低く、水を水素と酸素に完全に分解することができる水分解用光触媒、或いは高い活性を有する有機物分解用光触媒触媒、及び光合成反応の光触媒等として極めて有用である。 The photocatalyst obtained in the present invention has low toxicity and is extremely useful as a photocatalyst for water decomposition that can completely decompose water into hydrogen and oxygen, or a photocatalyst catalyst for organic matter decomposition having high activity, and a photocatalyst for photosynthesis reaction. It is.
本発明の光触媒を製造する好ましい手順の例について、以下に説明する。
１）はじめに、粉末状の（１）酸化セリウムと（２）カルシウム、ストロンチウム、イットリウム、ランタンからなる群から選択された異種元素を含む化合物の１種又は２種以上を、（２）異種元素の添加量が（１）酸化セリウムを基準として０．１〜５０モル％の範囲で混合して前駆体を得る。
１’）別法として、（１）硝酸セリウムあるいは塩化セリウムと、（２）ストロンチウム、カルシウム、イットリウム、ランタンからなる群から選択された異種元素を含むの水溶性化合物を、（２）異種元素の添加量が（１）セリウム化合物を基準として０．１〜５０モル％の範囲で水に溶解させ、ｐＨを７以上に調製して得られた沈殿を前駆体とすることもできる。
An example of a preferred procedure for producing the photocatalyst of the present invention will be described below.
1) First, one or more kinds of compounds containing different elements selected from the group consisting of (1) cerium oxide and (2) calcium, strontium, yttrium, and lanthanum in the form of powder; (2) The precursor is obtained by mixing the addition amount in the range of 0.1 to 50 mol% based on (1) cerium oxide.
1 ′) Alternatively, a water-soluble compound containing (1) cerium nitrate or cerium chloride and (2) a heterogeneous element selected from the group consisting of strontium, calcium, yttrium and lanthanum, (2) A precipitate obtained by dissolving in water in an amount of 0.1 to 50 mol% based on the cerium compound (1) and adjusting the pH to 7 or more can be used as a precursor.
２）次に、前駆体を空気中、５００〜１４００℃の温度に加熱する。
３）得られた（１）酸化セリウム及び（２）異種元素からなる複合体に、複合体を基準として０．１〜１０重量％程度になるように、酸化ルテニウム、又は白金から選択された助触媒を担持させることによって光触媒を構成する。前記以外の助触媒としては、酸化ニッケル、酸化コバルト、酸化クロム、酸化ロジウム、酸化イリジウム、或いは金等を使用することも可能である。
また、助触媒を担持する方法としては、上記の浸漬による方法の他に、光照射によって生じる励起電子を用いた光電着法を使用することも可能である。
2) Next, the precursor is heated to a temperature of 500 to 1400 ° C. in air.
3) In the obtained composite composed of (1) cerium oxide and (2) different elements, an assistant selected from ruthenium oxide or platinum so as to be about 0.1 to 10% by weight based on the composite. A photocatalyst is formed by supporting the catalyst. As a promoter other than the above, nickel oxide, cobalt oxide, chromium oxide, rhodium oxide, iridium oxide, gold, or the like can be used.
Moreover, as a method for supporting the cocatalyst, it is also possible to use a photo-deposition method using excited electrons generated by light irradiation in addition to the above-described method by immersion.
次に本発明の光触媒を製造する方法ついて実施例によりさらに詳細に説明するが、以下の具体例は本発明を限定するものではない。
以下の例では、光触媒の性能は水分解反応に対する水素と酸素の生成活性、および有害物質分解の代表例としてメチレンブルーの分解活性により評価した。
（実施例1）
粉末状の酸化セリウムと炭酸ストロンチウムを、セリウムに対してストロンチウム元素を１０％のモル比で混合し、大気中で、１０００℃の温度で１０時間焼成した。得られた複合体のＸ線回折パターンを図４に、紫外可視拡散反射スペクトルを図５に、そして発光スペクトルを図６に示す。
Next, the method for producing the photocatalyst of the present invention will be described in more detail by way of examples. However, the following specific examples do not limit the present invention.
In the following examples, the performance of the photocatalyst was evaluated by hydrogen and oxygen generation activity for water splitting reaction and methylene blue decomposition activity as a representative example of harmful substance decomposition.
(Example 1)
Powdered cerium oxide and strontium carbonate were mixed with a strontium element at a molar ratio of 10% with respect to cerium, and calcined in the atmosphere at a temperature of 1000 ° C. for 10 hours. The X-ray diffraction pattern of the obtained composite is shown in FIG. 4, the ultraviolet-visible diffuse reflection spectrum is shown in FIG. 5, and the emission spectrum is shown in FIG.
図４のＸ線回折パターンによると、ストロンチウム添加酸化セリウムは酸化セリウムと同様な結晶構造を有し、ほぼ単一相であること、および高い結晶性を有することが判る。また、図５の可視紫外拡散反射スペクトルから、ストロンチウムを添加した酸化セリウムの光吸収特性は、酸化セリウムとほぼ一致し、吸収端は４５０ｎｍ付近であることが判る。そして、図６の発光スペクトルから、ストロンチウムを添加することにより、４７０ｎｍ付近に発光ピークが出現し、その励起スペクトルの最大波長は２７５ｎｍであることが判る。 According to the X-ray diffraction pattern of FIG. 4, it can be seen that strontium-added cerium oxide has a crystal structure similar to that of cerium oxide, is almost single phase, and has high crystallinity. Further, from the visible ultraviolet diffuse reflection spectrum of FIG. 5, it can be seen that the light absorption characteristics of cerium oxide to which strontium is added are almost the same as those of cerium oxide, and the absorption edge is around 450 nm. From the emission spectrum of FIG. 6, it can be seen that by adding strontium, an emission peak appears in the vicinity of 470 nm, and the maximum wavelength of the excitation spectrum is 275 nm.
このストロンチウム添加酸化セリウム複合体１．０００ｇとトリルテニウムドデカカルボニル０．０２１０ｇをテトラヒドロフラン３０ｍLに溶かし、６０℃の温度で４時間還流した後に、空気中で４時間焼成して光触媒を得た（複合体を基準として、助触媒酸化ルテニウム１．０重量％を担持）。 1.100 g of this strontium-added cerium oxide complex and 0.0210 g of triruthenium dodecacarbonyl were dissolved in 30 mL of tetrahydrofuran, refluxed at 60 ° C. for 4 hours, and then calcined in air for 4 hours to obtain a photocatalyst (composite) On the basis of 1.0% by weight of the cocatalyst ruthenium oxide).
（光触媒の水分解活性）
このようにして作製した酸化ルテニウム担持酸化セリウム０．８ｇを蒸留水７００ｍＬ中に懸濁させ、４５０Ｗ高圧水銀ランプを光源として円筒型石英製ジャケットを通して光を照射した。その結果を図１に示す。
図１に見られるように、光照射によって水素と酸素がほぼ化学量論比で生成することが判った。反応初期の水素と酸素の生成活性は１１９μｍｏｌ/時間、５８μｍｏｌ/時間であった。３時間の光照射後、生成した水素と酸素を真空排気し、再び光照射を行うと水素と酸素の生成が見られたが、生成活性は低下した。しかし、４回目以降は、安定な水素と酸素の生成活性が見られた。この時の水素および酸素の生成活性はそれぞれ４７μｍｏｌ/時間、２３μｍｏｌ/時間となった。
(Water catalytic activity of photocatalyst)
The thus prepared ruthenium oxide-supporting cerium oxide (0.8 g) was suspended in 700 mL of distilled water, and irradiated with light through a cylindrical quartz jacket using a 450 W high-pressure mercury lamp as a light source. The result is shown in FIG.
As can be seen in FIG. 1, it was found that hydrogen and oxygen were produced in a substantially stoichiometric ratio by light irradiation. The production activity of hydrogen and oxygen at the beginning of the reaction was 119 μmol / hour and 58 μmol / hour. After 3 hours of light irradiation, the produced hydrogen and oxygen were evacuated and irradiated again to produce hydrogen and oxygen, but the production activity decreased. However, after the fourth time, stable hydrogen and oxygen generation activity was observed. At this time, the production activities of hydrogen and oxygen were 47 μmol / hour and 23 μmol / hour, respectively.
（比較例1）
上記実施例１において、ストロンチウムを添加していない酸化セリウムを用いて、大気中で、１０００℃の温度で１０時間焼成した以外は、実施例１と同様にして助触媒として
酸化ルテニウムを担持した光触媒を得た。この光触媒に同様に光を照射した結果を図３に示す。図３の左端に見られるように、水素０μｍｏｌ/時間、酸素０μｍｏｌ/時間の生成活性を示し、水分解活性を有しないことが判明した。
一方、実施例１において、酸化ルテニウムを担持する前のストロンチウム添加酸化セリウムに、同様に光照射したところ、水分解活性を示さなかった。
(Comparative Example 1)
A photocatalyst carrying ruthenium oxide as a co-catalyst in the same manner as in Example 1 except that cerium oxide to which strontium was not added was used and calcined in the atmosphere at a temperature of 1000 ° C. for 10 hours. Got. The result of irradiating the photocatalyst in the same manner is shown in FIG. As can be seen from the left end of FIG. 3, it was found that the production activity was 0 μmol / hour for hydrogen and 0 μmol / hour for oxygen, and there was no water splitting activity.
On the other hand, in Example 1, when strontium-added cerium oxide before carrying ruthenium oxide was similarly irradiated with light, it did not show water splitting activity.
（実施例２）
粉末状の酸化セリウムと炭酸ストロンチウムを、セリウムに対してストロンチウム元素のモル比が０〜５０％の範囲で混合し、大気中で、１０００℃の温度で１０時間焼成した。得られた焼成体に、実施例１と同様な方法で酸化ルテニウムを１．０重量％の割合で担持して、光触媒を作製した。これらの光触媒に、同様に光を照射した結果を図２示す。
図２に見られるように、ストロンチウムの添加量を変えることにより、水素と酸素の生成活性が変化することが判った。酸化セリウムに対して、ストロンチウムを１０％のモル比で添加した光触媒が最も高い生成活性を示し、１０％以上の添加量では活性が単調に減少することが判った。
(Example 2)
Powdered cerium oxide and strontium carbonate were mixed at a molar ratio of strontium element to cerium in the range of 0 to 50%, and calcined in the atmosphere at a temperature of 1000 ° C. for 10 hours. On the obtained fired body, ruthenium oxide was supported at a ratio of 1.0% by weight in the same manner as in Example 1 to produce a photocatalyst. The results of irradiating these photocatalysts similarly are shown in FIG.
As shown in FIG. 2, it was found that the generation activity of hydrogen and oxygen changes by changing the amount of strontium added. It was found that the photocatalyst added with strontium at a molar ratio of 10% showed the highest production activity with respect to cerium oxide, and the activity decreased monotonously at an addition amount of 10% or more.
（実施例３及び比較例２）
粉末状の酸化セリウムに、ストロンチウムと同様に２価の価数をとるカルシウム、マグネシウム、バリウム、亜鉛、鉛の炭酸塩あるいは酸化物を、セリウムに対してそれぞれの元素のモル比が１０％となるように混合し、大気中で、１０００℃の温度で１０時間焼成した。ついで、実施例１と同様な方法で酸化ルテニウムを１．０重量％で担持して、光触媒を得た。これらの光触媒に、同様に光を照射した結果を図３に示す。
(Example 3 and Comparative Example 2)
Like strontium, powdered cerium oxide has a divalent calcium, magnesium, barium, zinc, lead carbonate or oxide, and the molar ratio of each element to cerium is 10%. And were fired in the atmosphere at a temperature of 1000 ° C. for 10 hours. Subsequently, ruthenium oxide was supported at 1.0% by weight in the same manner as in Example 1 to obtain a photocatalyst. The results of irradiating these photocatalysts similarly are shown in FIG.
カルシウムを添加した酸化セリウムは、ストロンチウムを添加した酸化セリウムと同様に水分解反応に対して活性を示し、安定な水素と酸素の生成が見られた。水素および酸素の生成活性はそれぞれ３２μｍｏｌ/時間、１７μｍｏｌ/時間であった。
一方、マグネシウム、バリウム、亜鉛、鉛を添加した酸化セリウムは、化学量論比で水素と酸素を生成させる光触媒機能を有しなかった。
The cerium oxide to which calcium was added showed activity against the water splitting reaction in the same manner as the cerium oxide to which strontium was added, and stable generation of hydrogen and oxygen was observed. The production activities of hydrogen and oxygen were 32 μmol / hour and 17 μmol / hour, respectively.
On the other hand, cerium oxide added with magnesium, barium, zinc, and lead did not have a photocatalytic function for generating hydrogen and oxygen in a stoichiometric ratio.
（実施例4）
粉末状の酸化セリウムに３価のランタンを含有する酸化ランタンを、セリウムに対してランタン元素のモル比が１０％となるように混合し、大気中で、１０００℃の温度で１０時間焼成した。ついで、実施例１と同様な方法で酸化ルテニウムを１．０重量％で担持して、光触媒を得た。この光触媒に、同様に光を照射した結果を図７示す。
図７に見られるように反応初期から安定に水素および酸素が生成した。３時間の光照射後、生成した水素および酸素を真空排気して反応を繰り返したが、活性は変化しなかった。この時の水素および酸素の生成活性はそれぞれ２０５μｍｏｌ/時間、１０１μｍｏｌ/時間であった。
(Example 4)
Lanthanum oxide containing trivalent lanthanum in powdered cerium oxide was mixed so that the molar ratio of lanthanum element to cerium was 10%, and baked in air at a temperature of 1000 ° C. for 10 hours. Subsequently, ruthenium oxide was supported at 1.0% by weight in the same manner as in Example 1 to obtain a photocatalyst. FIG. 7 shows the result of similarly irradiating the photocatalyst with light.
As seen in FIG. 7, hydrogen and oxygen were stably generated from the beginning of the reaction. After irradiation for 3 hours, the generated hydrogen and oxygen were evacuated and the reaction was repeated, but the activity did not change. At this time, the production activities of hydrogen and oxygen were 205 μmol / hour and 101 μmol / hour, respectively.
（実施例５及び比較例３）
粉末状の酸化セリウムに、ランタンと同様に３価の価数をするイットリウム、エルビウム、インジウム、アンチモンの炭酸塩あるいは酸化物を、セリウムに対してそれぞれの元素のモル比が１０％となるように混合し、大気中で、１０００℃の温度で１０時間焼成した。ついで、実施例１と同様な方法で酸化ルテニウムを１．０重量％で担持して、光触媒を得た。これらの光触媒に、同様に光を照射した結果を図８に示す。
(Example 5 and Comparative Example 3)
Powdered cerium oxide is mixed with yttrium, erbium, indium, antimony carbonate or oxide having trivalent valence like lanthanum so that the molar ratio of each element to cerium is 10%. The mixture was mixed and baked in the air at a temperature of 1000 ° C. for 10 hours. Subsequently, ruthenium oxide was supported at 1.0% by weight in the same manner as in Example 1 to obtain a photocatalyst. The results of irradiating these photocatalysts similarly are shown in FIG.
イットリウムを添加した酸化セリウムは、ランタンを添加した酸化セリウムと同様に水分解反応に対して活性を示した。水素および酸素の生成活性はそれぞれ４５μｍｏｌ/時間、１９μｍｏｌ/時間であった。
一方、エルビウム、インジウム、アンチモンを添加した酸化セリウムは化学量論比で水素と酸素を生成させる光触媒機能を有しなかった。
Cerium oxide to which yttrium was added showed activity for water splitting reaction as cerium oxide to which lanthanum was added. The production activities of hydrogen and oxygen were 45 μmol / hour and 19 μmol / hour, respectively.
On the other hand, cerium oxide to which erbium, indium, and antimony were added did not have a photocatalytic function for generating hydrogen and oxygen in a stoichiometric ratio.
（実施例６）
粉末状の塩化セリウムとストロンチウムの塩化物を、セリウムに対してストロンチウム元素を１０％のモル比で水に溶解させ、水酸化ナトリウムを滴下して得られた沈殿を前駆体とした。この前駆体を大気中、１０００℃の温度で１０時間焼成した。ついで、実施例１と同様な方法で酸化ルテニウムを１．０重量％で担持して、光触媒を得た。この光触媒に、同様に光を照射したところ、実施例１と同様に水素と酸素が安定に生成した。
(Example 6)
Powdered cerium chloride and strontium chloride were dissolved in water at a molar ratio of 10% of strontium element to cerium, and sodium hydroxide was added dropwise as a precursor. This precursor was calcined in the atmosphere at a temperature of 1000 ° C. for 10 hours. Subsequently, ruthenium oxide was supported at 1.0% by weight in the same manner as in Example 1 to obtain a photocatalyst. When this photocatalyst was irradiated with light in the same manner, hydrogen and oxygen were stably generated as in Example 1.
（実施例７）
粉末状の酸化セリウムと酸化ランタンを、セリウムに対してランタン元素がモル比１０％となるように混合し、大気中で、１０００℃の温度で１０時間焼成した。このランタン添加酸化セリウムを蒸留水３０ｍＬに懸濁させ、ランタン添加酸化セリウムに対して白金元素が１．０重量％となるように濃度調整を行った塩化白金酸水溶液を加えた。ついで、外部照射型石英セル内にこの溶液を移し、２００Ｗ水銀キセノン光源により光を照射し、白金の光電着を行った後に、分離することにより光触媒を得た。
得られた白金担持ランタン添加酸化セリウムを、メチレンブルー３ｍｇを水１０００ｍｌに溶解させたメチレンブルー水溶液に懸濁させ、１時間の光照射を行った結果を図９に示す。
(Example 7)
Powdered cerium oxide and lanthanum oxide were mixed so that the lanthanum element had a molar ratio of 10% with respect to cerium, and baked in air at a temperature of 1000 ° C. for 10 hours. This lanthanum-added cerium oxide was suspended in 30 mL of distilled water, and a chloroplatinic acid aqueous solution whose concentration was adjusted so that the platinum element was 1.0 wt% with respect to the lanthanum-added cerium oxide was added. Next, this solution was transferred into an external irradiation type quartz cell, irradiated with light from a 200 W mercury xenon light source, subjected to photoelectron deposition of platinum, and then separated to obtain a photocatalyst.
The resulting platinum-supported lanthanum-added cerium oxide was suspended in a methylene blue aqueous solution in which 3 mg of methylene blue was dissolved in 1000 ml of water, and the result of light irradiation for 1 hour is shown in FIG.
また、白金を担持させる前のランタン添加酸化セリウムについても１時間の光照射を行いその結果を図９に示した。図９に見られるように、光照射により、ランタン添加酸化セリウムでは３６％、白金担持ランタン添加酸化セリウムでは１００％のメチレンブルーが分解した。 Also, lanthanum-added cerium oxide before carrying platinum was irradiated with light for 1 hour, and the result is shown in FIG. As seen in FIG. 9, 36% of methylene blue was decomposed by lanthanum-added cerium oxide and 100% of platinum-supported lanthanum-added cerium oxide by light irradiation.
本発明で得られた光触媒は、水の完全分解やメチレンブルーの分解のみならず、エタノールや油などの有機物質の分解、或いは排ガスなどに含まれる環境汚染物質の光分解反応や、各種の光合成反応等の幅広い分野にも適用可能なものである。さらには、本発明の光触媒の持つ低い毒性を生かして、医療用光触媒や環境用光触媒としての応用することができる。 The photocatalyst obtained in the present invention is not only the complete decomposition of water and the decomposition of methylene blue, but also the decomposition of organic substances such as ethanol and oil, or the photolysis reaction of environmental pollutants contained in exhaust gas, and various photosynthesis reactions. It can be applied to a wide range of fields. Furthermore, taking advantage of the low toxicity of the photocatalyst of the present invention, it can be applied as a medical photocatalyst or an environmental photocatalyst.
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| JP2002263449A (en) * | 2001-03-09 | 2002-09-17 | Equos Research Co Ltd | Activated carbon filter |
| JP2002301369A (en) * | 2001-04-10 | 2002-10-15 | Japan Science & Technology Corp | PHOTOCATALYST USING OXIDE CONTAINING TYPICAL METALLIC ION IN d10 ELECTRONIC STATE |
| JP2003033662A (en) * | 2001-07-23 | 2003-02-04 | Sumitomo Metal Mining Co Ltd | Photocatalyst exhibiting catalytic activity in visible light region |
| JP2003047859A (en) * | 2001-08-08 | 2003-02-18 | Sumitomo Metal Mining Co Ltd | Photocatalyst having catalytic activity even in visible light region |
| JP2003251197A (en) * | 2002-03-06 | 2003-09-09 | National Institute For Materials Science | Visible light responding photocatalyst comprising rare- earth element, hydrogen manufacturing method using the same and decomposition method for harmful chemical substance |
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2006
- 2006-12-22 JP JP2006345205A patent/JP5034046B2/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002263449A (en) * | 2001-03-09 | 2002-09-17 | Equos Research Co Ltd | Activated carbon filter |
| JP2002301369A (en) * | 2001-04-10 | 2002-10-15 | Japan Science & Technology Corp | PHOTOCATALYST USING OXIDE CONTAINING TYPICAL METALLIC ION IN d10 ELECTRONIC STATE |
| JP2003033662A (en) * | 2001-07-23 | 2003-02-04 | Sumitomo Metal Mining Co Ltd | Photocatalyst exhibiting catalytic activity in visible light region |
| JP2003047859A (en) * | 2001-08-08 | 2003-02-18 | Sumitomo Metal Mining Co Ltd | Photocatalyst having catalytic activity even in visible light region |
| JP2003251197A (en) * | 2002-03-06 | 2003-09-09 | National Institute For Materials Science | Visible light responding photocatalyst comprising rare- earth element, hydrogen manufacturing method using the same and decomposition method for harmful chemical substance |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015071699A (en) * | 2013-10-03 | 2015-04-16 | 日本電気硝子株式会社 | Wavelength conversion material, wavelength conversion member and light-emitting device |
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| JP5034046B2 (en) | 2012-09-26 |
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