JP2013230427A - Photocatalyst, and method for manufacturing the same - Google Patents
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- 238000000034 method Methods 0.000 title abstract description 24
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- WQNHWIYLCRZRLR-UHFFFAOYSA-N 2-(3-hydroxy-2,5-dioxooxolan-3-yl)acetic acid Chemical compound OC(=O)CC1(O)CC(=O)OC1=O WQNHWIYLCRZRLR-UHFFFAOYSA-N 0.000 description 2
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- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical class [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
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- 241000282326 Felis catus Species 0.000 description 1
- 241000511976 Hoya Species 0.000 description 1
- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
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Images
Abstract
Description
本発明は、太陽光を利用した水分解反応を行うことにより水素および／または酸素を製造可能な光水分解反応に特に好適に用いられる光触媒およびその製造方法に関する。 The present invention relates to a photocatalyst that is particularly preferably used in a photowater splitting reaction that can produce hydrogen and / or oxygen by performing a water splitting reaction using sunlight.
太陽エネルギーなどの再生可能エネルギーを利用した高性能な光エネルギー変換システムを実用化することは、地球温暖化の抑制、および枯渇しつつある化石資源依存からの脱却を目指す観点から、近年になって急激にその重要性が増している。中でも、太陽エネルギーを用いて水を分解し水素を製造する技術は、現行の石油精製、アンモニア、メタノールの原料供給技術としてのみならず、燃料電池をベースとした来たる水素エネルギー社会において、必須とされる技術である。 In recent years, the practical application of high-performance light energy conversion systems that use renewable energy such as solar energy has been aimed at controlling global warming and moving away from the depletion of fossil resources. Its importance is increasing rapidly. Above all, the technology that decomposes water using solar energy to produce hydrogen is indispensable not only in the current petroleum refining, ammonia and methanol raw material supply technology, but also in the future hydrogen energy society based on fuel cells. Technology.
例えば、光触媒を用いることで、太陽エネルギーを利用して水を分解し、効率的に水素や酸素を製造することができる（非特許文献１等）。有望な光触媒の一つとしては、可視光応答型の水分解用光触媒であるＴｉやＮｂを含む酸窒化物が挙げられる。 For example, by using a photocatalyst, water can be decomposed using solar energy, and hydrogen and oxygen can be produced efficiently (Non-Patent Document 1, etc.). One promising photocatalyst is an oxynitride containing Ti or Nb, which is a visible light responsive photocatalyst for water splitting.
このような酸窒化物は、単独では水分解活性が小さいため、通常、助触媒を担持して使用される。助触媒としては、高活性であり且つ安定である理由から、通常、ＩｒＯ２、ＲｕＯ２、Ｐｔなどの貴金属触媒が使用される。
しかしながら、地表埋蔵量が極めて少なく高価な貴金属を使用することは好ましくない。また、貴金属助触媒を用いたとしても、必ずしも水分解活性が十分であるとは言えない。
Since such oxynitride alone has a small water splitting activity, it is usually used by supporting a promoter. As the cocatalyst, a noble metal catalyst such as IrO 2 , RuO 2 , or Pt is usually used because it is highly active and stable.
However, it is not preferable to use an expensive noble metal with a very small surface reserve. Moreover, even if a noble metal promoter is used, it cannot be said that the water splitting activity is sufficient.
一方、非貴金属助触媒としては、例えば酸素発生用助触媒としてＣｏ３Ｏ４、ＭｎＯｘ、ＮｉＯｘ、ＮｉＣｏ２Ｏ４等が比較的高活性であることが知られている（非特許文献２、３等）。
しかしながら、非貴金属助触媒は貴金属助触媒に比べると活性が劣る。そのため、貴金属助触媒と同等以上の水分解活性を示すような非貴金属助触媒が求められている。
On the other hand, as non-noble metal promoters, for example, Co 3 O 4 , MnO x , NiO x , NiCo 2 O 4 and the like as oxygen promoters are known to have relatively high activity (Non-patent Document 2). 3 etc.).
However, non-noble metal promoters are less active than noble metal promoters. Therefore, a non-noble metal promoter that exhibits a water splitting activity equal to or higher than that of the noble metal promoter is required.
そこで本発明は、資源が豊富で比較的安価な材料より製造される光触媒用助触媒を有するとともに、貴金属助触媒を担持した場合と同等以上の水分解活性を示す光触媒およびその製造方法を提供することを課題とする。 Accordingly, the present invention provides a photocatalyst having a photocatalyst cocatalyst produced from a resource-rich and relatively inexpensive material, and exhibiting a water splitting activity equivalent to or higher than that when a noble metal cocatalyst is supported, and a method for producing the photocatalyst. This is the issue.
本発明者らは、上記の課題を解決すべく鋭意検討した結果、以下の知見を得た。
（１）Ｔｉおよび／またはＮｂを含む酸窒化物に非貴金属助触媒を担持した場合、貴金属助触媒を担持した場合と同等の水分解活性を有する。
（２）Ｔｉおよび／またはＮｂを含む酸窒化物に担持する非貴金属助触媒において、金属酸化物ＭＯｘと金属Ｍとを混在させた場合、水分解活性が一層向上する。
（３）特に、Ｔｉおよび／またはＮｂを含む酸窒化物に、金属元素Ｍを含む化合物を担持させた後、当該金属元素Ｍを含む化合物を還元処理して金属Ｍおよび金属酸化物ＭＯｘとすることで、極めて高活性な光触媒を得ることができる。
As a result of intensive studies to solve the above problems, the present inventors have obtained the following knowledge.
(1) When a non-noble metal promoter is supported on an oxynitride containing Ti and / or Nb, the water splitting activity is equivalent to that when a noble metal promoter is supported.
(2) In the non-noble metal promoter supported on the oxynitride containing Ti and / or Nb, when the metal oxide MO x and the metal M are mixed, the water splitting activity is further improved.
(3) In particular, after a compound containing a metal element M is supported on an oxynitride containing Ti and / or Nb, the compound containing the metal element M is subjected to a reduction treatment to obtain a metal M and a metal oxide MO x By doing so, an extremely highly active photocatalyst can be obtained.
本発明は上記の知見に基づいてなされたものである。すなわち、
第１の本発明は、Ｔｉおよび／またはＮｂを含む酸窒化物に、ＭＯｘで表される金属酸化物および金属Ｍを助触媒として担持したことを特徴とする、光触媒である。
The present invention has been made based on the above findings. That is,
A first aspect of the present invention is a photocatalyst characterized in that a metal oxide represented by MO x and a metal M are supported as promoters on an oxynitride containing Ti and / or Nb.
第１の本発明において、酸窒化物が、ＬａＴｉＯ２Ｎ、ＣａＮｂＯ２Ｎ、ＢａＮｂＯ２Ｎ、ＳｒＮｂＯ２Ｎ、ＬａＮｂＯ２Ｎから選ばれる少なくとも１種であることが好ましい。これら酸窒化物を用いた場合に、ＭＯｘで表される金属酸化物および金属Ｍを助触媒とした場合の触媒活性向上効果が一層顕著となるためである。 In the first aspect of the present invention, the oxynitride is preferably at least one selected from LaTiO 2 N, CaNbO 2 N, BaNbO 2 N, SrNbO 2 N, and LaNbO 2 N. This is because when these oxynitrides are used, the effect of improving the catalytic activity when the metal oxide represented by MO x and the metal M are used as promoters becomes more remarkable.
第１の本発明において、助触媒が、金属酸化物と金属とのコアシェル型構造を有することが好ましい。このような構造とすると、結果的に触媒活性向上効果が一層顕著となる。 In the first aspect of the present invention, the promoter preferably has a core-shell structure of a metal oxide and a metal. With such a structure, as a result, the effect of improving the catalytic activity becomes more remarkable.
第１の本発明において、助触媒を構成する金属元素Ｍが、コバルト、ニッケル、マンガンから選ばれる少なくとも１つであることが好ましい。このような金属を用いた場合に、特に触媒活性向上効果が得られるためである。 In the first aspect of the present invention, the metal element M constituting the promoter is preferably at least one selected from cobalt, nickel, and manganese. This is because when such a metal is used, an effect of improving the catalytic activity can be obtained.
第２の本発明は、Ｔｉおよび／またはＮｂを含む酸窒化物に、ＭＯｘで表される金属酸化物および金属Ｍを助触媒として担持してなる光触媒の製造方法であって、Ｔｉおよび／またはＮｂを含む酸窒化物に、金属元素Ｍを含む化合物を担持させる第１の工程と、金属元素Ｍを含む化合物を還元処理する第２の工程と、を含むことを特徴とする、光触媒の製造方法である。 A second aspect of the present invention is a method for producing a photocatalyst comprising a metal oxide represented by MO x and a metal M supported as promoters on an oxynitride containing Ti and / or Nb, wherein Ti and / Or a first step of supporting a compound containing the metal element M on an oxynitride containing Nb, and a second step of reducing the compound containing the metal element M. It is a manufacturing method.
第２の本発明において、酸窒化物が、ＬａＴｉＯ２Ｎ、ＣａＮｂＯ２Ｎ、ＢａＮｂＯ２Ｎ、ＳｒＮｂＯ２Ｎ、ＬａＮｂＯ２Ｎから選ばれる少なくとも１種であることが好ましい。 In the second aspect of the present invention, the oxynitride is preferably at least one selected from LaTiO 2 N, CaNbO 2 N, BaNbO 2 N, SrNbO 2 N, and LaNbO 2 N.
第２の本発明において、助触媒を構成する金属元素Ｍがコバルト、ニッケル、マンガンから選ばれる少なくとも１つであることが好ましい。 In the second aspect of the present invention, the metal element M constituting the promoter is preferably at least one selected from cobalt, nickel, and manganese.
第２の本発明において、還元処理が、還元性気体による処理であることが好ましい。 In the second aspect of the present invention, the reduction treatment is preferably treatment with a reducing gas.
ここで「還元性気体」とは金属元素Ｍを含む化合物を還元して金属Ｍとすることが可能な気体を意味する。還元性気体の具体例としては、例えば、アンモニア、水素、ヒドラジンが挙げられる。「還元性気体による処理」とは、還元性気体により金属元素Ｍを含む化合物を還元して金属とすることが可能な処理であればよく、例えば金属元素Ｍを含む化合物を加熱しつつ還元性気体により還元処理する形態が挙げられる。 Here, the “reducing gas” means a gas capable of reducing a compound containing the metal element M to the metal M. Specific examples of the reducing gas include ammonia, hydrogen, and hydrazine. The “treatment with a reducing gas” may be any treatment that can reduce a compound containing the metal element M to a metal with the reducing gas, for example, reducing the compound containing the metal element M while heating it. The form which carries out a reduction process with gas is mentioned.
第１の本発明においては、Ｔｉおよび／またはＮｂを含む酸窒化物に、ＭＯｘで表される金属酸化物および金属Ｍを助触媒として担持したことにより、貴金属を助触媒として担持した場合と同等以上の水分解活性を示す光触媒とすることができる。このような光触媒は、例えば第２の本発明に係る光触媒の製造方法により、複雑な工程を要さずに適切に製造することができる。すなわち、本発明によれば、資源が豊富で比較的安価な材料より製造される光触媒用助触媒を有するとともに、貴金属助触媒を担持した場合と同等以上の水分解活性を示す光触媒およびその製造方法を提供することができる。 In the first aspect of the present invention, a metal oxide represented by MO x and a metal M are supported as promoters on an oxynitride containing Ti and / or Nb, thereby supporting a noble metal as a promoter. It can be set as the photocatalyst which shows the water splitting activity more than equivalent. Such a photocatalyst can be appropriately manufactured without requiring a complicated process by, for example, the photocatalyst manufacturing method according to the second aspect of the present invention. That is, according to the present invention, a photocatalyst having a photocatalyst cocatalyst produced from a resource-rich and relatively inexpensive material and exhibiting a water splitting activity equivalent to or higher than that when a noble metal cocatalyst is supported, and a production method thereof Can be provided.
１．光触媒
本発明に係る光触媒は、Ｔｉおよび／またはＮｂを含む酸窒化物に、ＭＯｘで表される金属酸化物および金属Ｍを助触媒として担持したことに特徴を有する。
1. Photocatalyst The photocatalyst according to the present invention is characterized in that a metal oxide represented by MO x and a metal M are supported as promoters on an oxynitride containing Ti and / or Nb.
１．１．酸窒化物
Ｔｉおよび／またはＮｂを含む酸窒化物としては、光触媒として機能し得る酸窒化物であれば特に限定されるものではなく、例えば、希土類金属および／またはアルカリ土類金属とＴｉおよび／またはＮｂとの複合酸窒化物等が挙げられ、より具体的にはＬａＴｉＯ２Ｎ、ＣａＮｂＯ２Ｎ、ＢａＮｂＯ２Ｎ、ＳｒＮｂＯ２Ｎ、ＬａＮｂＯ２Ｎ等が挙げられる。この中でもＬａＴｉＯ２Ｎ、ＳｒＮｂＯ２Ｎ、ＣａＮｂＯ２Ｎのいずれか１つ以上が好ましく、ＬａＴｉＯ２Ｎが特に好ましい。本発明による水分解活性向上効果が特に顕著となるためである。
1.1. The oxynitride containing Ti and / or Nb is not particularly limited as long as it is an oxynitride that can function as a photocatalyst. For example, rare earth metal and / or alkaline earth metal and Ti and / or Alternatively, complex oxynitrides with Nb and the like can be mentioned, and more specifically, LaTiO 2 N, CaNbO 2 N, BaNbO 2 N, SrNbO 2 N, LaNbO 2 N and the like can be mentioned. Among these, any one or more of LaTiO 2 N, SrNbO 2 N, and CaNbO 2 N are preferable, and LaTiO 2 N is particularly preferable. This is because the effect of improving water splitting activity according to the present invention is particularly remarkable.
本発明において、Ｔｉおよび／またはＮｂを含む酸窒化物は、公知の方法により容易に得ることができる。例えば、固相法やゾル・ゲル法、錯体重合法、フラックス法等の複合酸化物を得るための公知の方法によりＴｉおよび／またはＮｂを含む複合酸化物を得て、当該複合酸化物に対して、アンモニア雰囲気で高温処理すること等の窒化処理を施すことにより、Ｔｉおよび／またはＮｂを含む酸窒化物を得ることができる。 In the present invention, the oxynitride containing Ti and / or Nb can be easily obtained by a known method. For example, a composite oxide containing Ti and / or Nb is obtained by a known method for obtaining a composite oxide such as a solid phase method, a sol-gel method, a complex polymerization method, a flux method, etc. Thus, oxynitride containing Ti and / or Nb can be obtained by performing nitriding such as high temperature treatment in an ammonia atmosphere.
１．２．助触媒
本発明においては上記したような酸窒化物に、ＭＯｘで表される金属酸化物および金属Ｍの双方が助触媒として担持されている。助触媒を構成する金属Ｍとしては、助触媒として機能し得る金属であればよいが、本発明においては貴金属以外の金属とする。酸化反応用の助触媒金属Ｍとしては、好ましくは、Ｍｇ、Ｔｉ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｇａ、Ｃｄ、Ｃｅ、Ｔａ、ＷまたはＰｂ等の金属、該金属の金属間化合物、固溶体、共晶体、該金属の多元金属粒子であり、より好ましくはＣｏ、Ｍｎ、Ｎｉのうちのいずれか１種以上であり、特にＣｏが好ましい。金属酸化物ＭＯｘとしては、これら金属Ｍの酸化物であればその形態は特に限定されない。例えば、ＣｏＯｘ（ＣｏＯ、Ｃｏ２Ｏ３、Ｃｏ３Ｏ４等）、ＭｎＯｘ（ＭｎＯ、ＭｎＯ２、Ｍｎ２Ｏ３、Ｍｎ３Ｏ４等）、ＮｉＯｘ（ＮｉＯ、ＮｉＯ２等）等の同一金属による構成される酸化物或いはその混合物のほか、ＮｉＣｏ２Ｏ４等の複合酸化物或いはその混合物であってもよい。
還元反応用の助触媒金属Ｍとしては、好ましくは、Ｆｅ、Ｎｉ、Ｃｕ、Ｃｒ、Ｃｏ等が挙げられる。特にＣｕ、Ｃｒ、Ｎｉが好ましい。
1.2. Cocatalyst In the present invention, both the metal oxide represented by MO x and the metal M are supported on the oxynitride as described above as a cocatalyst. The metal M constituting the promoter may be any metal that can function as a promoter, but in the present invention, it is a metal other than a noble metal. The promoter metal M for the oxidation reaction is preferably a metal such as Mg, Ti, Mn, Fe, Co, Ni, Cu, Ga, Cd, Ce, Ta, W or Pb, an intermetallic compound of the metal, Solid solution, eutectic, and multi-metal particles of the metal, more preferably one or more of Co, Mn, and Ni, with Co being particularly preferred. The form of the metal oxide MO x is not particularly limited as long as it is an oxide of these metals M. For example, CoO x (CoO, Co 2 O 3 , Co 3 O 4 etc.), MnO x (MnO, MnO 2 , Mn 2 O 3 , Mn 3 O 4 etc.), NiO x (NiO, NiO 2 etc.), etc. In addition to an oxide composed of the same metal or a mixture thereof, a composite oxide such as NiCo 2 O 4 or a mixture thereof may be used.
Preferred examples of the promoter metal M for the reduction reaction include Fe, Ni, Cu, Cr, Co and the like. Cu, Cr, and Ni are particularly preferable.
なお、本発明においては、助触媒として上記の金属酸化物ＭＯｘ、金属Ｍのほか、その他の助触媒が担持されていてもよい。例えば、ＮｉＳ、ＭｏＳ２、ＮｉＭｏＳ等の硫化物が挙げられる。 In the present invention, in addition to the above metal oxide MO x and metal M, other promoters may be supported as promoters. For example, sulfides such as NiS, MoS 2 and NiMoS can be used.
本発明においては、従来においては助触媒としての活性が十分ではないと考えられていた金属であっても、所定の酸窒化物に、金属酸化物と金属との双方が助触媒として担持された光触媒とすることで、助触媒として貴金属が担持された光触媒と同等以上の水分解活性を得ることができる。 In the present invention, both a metal oxide and a metal are supported as promoters on a predetermined oxynitride, even if the metal is conventionally considered to have insufficient activity as a promoter. By using a photocatalyst, water splitting activity equivalent to or higher than that of a photocatalyst carrying a noble metal as a promoter can be obtained.
本発明において、助触媒は金属Ｍと金属酸化物ＭＯｘとのコアシェル型構造となっていることが好ましい。この場合、通常、金属Ｍがコア、金属酸化物ＭＯｘがシェルを構成する。例えば、図１に示すように、酸窒化物であるＬａＴｉＯ２Ｎの表面に、ＣｏＯｘおよびＣｏのコアシェル型構造を有する助触媒が担持された形態が挙げられる。このような酸窒化物にコアシェル型構造を有する助触媒が担持された光触媒の製造方法については後述する。 In the present invention, it is preferred that the co-catalyst has a core-shell structure of a metal M and the metal oxide MO x. In this case, usually, the metal M constitutes the core and the metal oxide MO x constitutes the shell. For example, as shown in FIG. 1, a form in which a promoter having a core-shell structure of CoO x and Co is supported on the surface of LaTiO 2 N that is an oxynitride. A method for producing a photocatalyst in which a promoter having a core-shell structure is supported on such an oxynitride will be described later.
酸窒化物への助触媒の担持方法については、特に限定されるものではなく、公知の担持方法をいずれも適用することができる。例えば、助触媒となる金属源（金属元素Ｍを含む化合物）を含有する溶液やコロイド溶液に酸窒化物の粉体や成形体を浸漬し、蒸発乾固する、または金属Ｍのカルボニル化合物を昇華によって酸窒化物表面へ吸着させ、これを熱分解させることなどによって、酸窒化物の表面に助触媒を担持することができる。また、文献（ＰＮＡＳ ｖｏｌ．１０６，２０６３３−２０６３６（２００９））に記載されている、助触媒となる金属源のイオンを含有する溶液に、酸窒化物の粉体や成型体を浸漬し、光照射する方法により担持してもよい。 The method for supporting the cocatalyst on the oxynitride is not particularly limited, and any known supporting method can be applied. For example, oxynitride powder or compact is immersed in a solution or colloidal solution containing a metal source (compound containing metal element M) as a promoter, and evaporated to dryness, or a carbonyl compound of metal M is sublimated. The cocatalyst can be supported on the surface of the oxynitride by, for example, adsorbing it onto the oxynitride surface and thermally decomposing it. In addition, an oxynitride powder or a molded body is immersed in a solution containing ions of a metal source serving as a promoter described in a literature (PNAS vol. 106, 20633-20636 (2009)). You may carry | support by the method of irradiating.
助触媒の担持量については、少なすぎても効果がなく、多すぎると助触媒自身が光を吸収・散乱するなどして酸窒化物の光吸収を妨げたり、再結合中心として働いたりして、かえって触媒活性が低下してしまう。このような観点から、光触媒における助触媒の担持量は、特に限定はされないが、光触媒全体を基準（１００質量％）として、好ましくは０．０１質量％以上２０質量％以下であり、より好ましくは１５質量％以下、特に好ましくは１０質量％以下である。 If the amount of the cocatalyst supported is too small, there is no effect. If the amount is too large, the cocatalyst itself absorbs and scatters light, preventing the light absorption of the oxynitride or acting as a recombination center. On the contrary, the catalytic activity is lowered. From such a viewpoint, the amount of the cocatalyst supported in the photocatalyst is not particularly limited, but is preferably 0.01% by mass or more and 20% by mass or less, more preferably, based on the entire photocatalyst (100% by mass). It is 15 mass% or less, Most preferably, it is 10 mass% or less.
本発明に係る光触媒を実際に水の分解に使用する場合において、光触媒の形態については特に限定されるものではなく、水中に光触媒粒子を分散・懸濁させる形態であってもよいし、光触媒粒子を固めて成形体として、当該成形体を水中に設置する形態或いは基材上に光触媒層を設けて積層体とし、当該積層体を水中に設置する形態等であってもよい。 In the case where the photocatalyst according to the present invention is actually used for water decomposition, the form of the photocatalyst is not particularly limited, and may be a form in which the photocatalyst particles are dispersed and suspended in water. The molded body may be in a form in which the molded body is placed in water or in a form in which a photocatalyst layer is provided on a substrate to form a laminated body, and the laminated body is placed in water.
２．光触媒の製造方法
本発明に係る光触媒の製造方法は、Ｔｉおよび／またはＮｂを含む酸窒化物に、ＭＯｘで表される金属酸化物および金属Ｍを助触媒として担持してなる光触媒の製造方法であって、Ｔｉおよび／またはＮｂを含む酸窒化物に、金属元素Ｍを含む化合物を担持させる第１の工程と、金属元素Ｍを含む化合物を還元処理する第２の工程とを含むことを特徴とする。
2. Method for Producing Photocatalyst The method for producing a photocatalyst according to the present invention is a method for producing a photocatalyst comprising a metal oxide represented by MO x and a metal M supported as promoters on an oxynitride containing Ti and / or Nb. A first step of supporting a compound containing a metal element M on an oxynitride containing Ti and / or Nb and a second step of reducing the compound containing the metal element M. Features.
第１の工程は、Ｔｉおよび／またはＮｂを含む酸窒化物に、金属元素Ｍを含む化合物を担持させる工程である。 The first step is a step of supporting a compound containing the metal element M on an oxynitride containing Ti and / or Nb.
本発明における金属元素Ｍを含む化合物とは、後述する還元処理によって金属Ｍとなる化合物をいい、具体的には例えば、ＭＯｘで表される金属酸化物；硝酸塩、硫酸塩、炭酸塩、リン酸塩、ヘキサフルオロリン酸塩、ホウ酸塩、テトラフルオロホウ酸塩、ハロゲンオキソ酸塩、カルボン酸塩、スルホン酸塩等の金属元素Ｍを含む塩；アセチルアセトナート、カルボニル化合物等の金属元素Ｍを含む錯体化合物；金属Ｍのハロゲン化物；金属Ｍの表面が酸化されＭＯｘの表面皮膜がついたもの等が挙げられる。このうちＭＯｘで表される金属酸化物、または金属元素Ｍを含む塩が好ましい。金属元素Ｍを含む塩としては、溶解性、製造性の面で硝酸塩が好ましい。 The compound containing a metal element M in the present invention means a compound which is a metal M by reduction process described later, specifically, for example, metal oxide represented by MO x; nitrates, sulfates, carbonates, phosphates Salts containing metal elements M such as acid salts, hexafluorophosphates, borates, tetrafluoroborates, halogen oxoacid salts, carboxylates and sulfonates; metal elements such as acetylacetonates and carbonyl compounds M-containing complex compounds; metal M halides; metal M surface oxidized and MO x surface coating. Among these, a metal oxide represented by MO x or a salt containing the metal element M is preferable. As the salt containing the metal element M, nitrate is preferable in terms of solubility and manufacturability.
酸窒化物や金属元素Ｍを含む化合物の形態については、上記したものと同様である。酸窒化物の金属元素Ｍを含む化合物の担持方法も上述した通りであり特に限定されるものではない。例えば、助触媒となる金属源を含む水溶液に、酸窒化物粉体を浸漬・懸濁させ、溶媒を蒸発乾固する、金属Ｍのカルボニル化合物を昇華によって酸窒化物表面へ吸着させ、これを熱分解させることなどによって、酸窒化物の表面に金属元素Ｍを含む化合物を担持することができる。また助触媒となる金属源のイオンを含有する溶液に酸窒化物の粉体や成型体を浸漬し、光照射することにより担持してもよい。 The form of the compound containing oxynitride or metal element M is the same as described above. The method for supporting the compound containing the metal element M of oxynitride is also not particularly limited as described above. For example, the oxynitride powder is immersed and suspended in an aqueous solution containing a metal source that serves as a cocatalyst, and the solvent is evaporated to dryness. The metal M carbonyl compound is adsorbed on the oxynitride surface by sublimation. A compound containing the metal element M can be supported on the surface of the oxynitride by thermal decomposition or the like. Alternatively, the powder may be supported by immersing an oxynitride powder or molded body in a solution containing ions of a metal source serving as a promoter and irradiating with light.
なお、これら金属元素Ｍを含む化合物を担持した後、焼成処理をする工程を含んでいてもよい。具体的には金属元素Ｍを含む化合物として、溶解性が高い塩等の、均一性の高い溶液が得られるものを用いて酸窒化物に担持したのち、焼成処理を行う。助触媒を均一に担持できる点、金属元素Ｍを含む化合物中に含まれる塩化物イオン等の、後述する還元処理に際して残留が好ましくない成分の除去に有効である点で好ましい製造方法として挙げられる。 In addition, after carrying | supporting the compound containing these metal elements M, the process of baking processing may be included. Specifically, the compound containing the metal element M is supported on an oxynitride using a highly soluble solution such as a highly soluble salt, and then subjected to a firing treatment. It is mentioned as a preferable production method in that the cocatalyst can be supported uniformly and is effective in removing components such as chloride ions contained in the compound containing the metal element M that are not preferably retained in the reduction treatment described later.
第２の工程は、前記金属元素Ｍを含む化合物を還元処理する工程である。本発明者らが鋭意研究したところ、所定の酸窒化物表面に、助触媒としてまず金属元素Ｍを含む化合物を担持させ、その後、担持した金属元素Ｍを含む化合物を還元して金属Ｍとすることにより、光触媒活性が著しく向上することを知見した。この現象は後述する還元処理をすることにより、ＭＯｘで表される金属酸化物、または金属元素Ｍを含む塩等が還元され、金属Ｍに変換される。そして引き続き、金属Ｍの表面が酸化され、ＭＯｘで表される金属酸化物が表面に形成されることによって発現するものと推定される。これは種々の要因によるものと考えられるが、例えばその一つとして、酸窒化物に担持後の金属元素Ｍを含む化合物を還元して金属Ｍとすることで、酸窒化物表面と助触媒との界面に良好な接触が得られ、活性が向上したものと推測できる。または、助触媒と酸窒化物との接触界面が増大し、触媒活性が向上したものと推測することができる。 The second step is a step of reducing the compound containing the metal element M. As a result of extensive research by the present inventors, a compound containing a metal element M is first supported as a promoter on a predetermined oxynitride surface, and then the compound containing the supported metal element M is reduced to form a metal M. It has been found that the photocatalytic activity is remarkably improved. In this phenomenon, a metal oxide represented by MO x or a salt containing the metal element M is reduced and converted to the metal M by performing a reduction treatment described later. Subsequently, it is presumed that the surface of the metal M is oxidized, and a metal oxide represented by MO x is formed on the surface. This is considered to be due to various factors. For example, by reducing the compound containing the metal element M after being supported on the oxynitride to the metal M, the oxynitride surface, the promoter, It can be inferred that good contact was obtained at the interface and the activity was improved. Alternatively, it can be presumed that the contact interface between the cocatalyst and the oxynitride is increased and the catalytic activity is improved.
第２の工程における還元処理については、金属元素Ｍを含む化合物を金属Ｍへと還元することが可能な処理であれば特に限定されるものではないが、還元性気体による処理であることが好ましい。還元性気体としては、例えば、アンモニア、水素、ヒドラジンが挙げられる。特にアンモニアが好ましい。還元処理の温度については、好ましくは５００℃以上、より好ましくは６００℃以上とし、好ましくは９００℃以下、より好ましくは８００℃以下とする。還元処理の時間については特に限定されるものではないが、好ましくは０．５時間以上、より好ましくは１時間以上とし、好ましくは２０時間以下、より好ましくは１０時間以下とする。このような温度・時間とすることで、酸窒化物表面において金属元素Ｍを含む化合物を適切に金属Ｍに還元でき、光触媒活性を一層増大させることができる。 The reduction treatment in the second step is not particularly limited as long as it is a treatment capable of reducing the compound containing the metal element M to the metal M, but is preferably a treatment with a reducing gas. . Examples of the reducing gas include ammonia, hydrogen, and hydrazine. Ammonia is particularly preferable. The temperature of the reduction treatment is preferably 500 ° C. or higher, more preferably 600 ° C. or higher, preferably 900 ° C. or lower, more preferably 800 ° C. or lower. The time for the reduction treatment is not particularly limited, but is preferably 0.5 hours or longer, more preferably 1 hour or longer, preferably 20 hours or shorter, more preferably 10 hours or shorter. By setting such temperature and time, the compound containing the metal element M on the oxynitride surface can be appropriately reduced to the metal M, and the photocatalytic activity can be further increased.
第２の工程を経ることで、酸窒化物の表面に還元された金属が助触媒として担持された光触媒が得られる。その後、金属表面は自ずと酸化され金属酸化物層となる。すなわち、本発明に係る光触媒の製造方法により得られた光触媒は、酸窒化物の表面に、金属酸化物と金属とのコアシェル型構造（コア：金属、シェル：金属酸化物）を有する助触媒が担持されていると言える（例えば図１参照）。このような光触媒は、貴金属を助触媒として担持した場合と比較して同等以上の光触媒活性を有する。 By passing through the second step, a photocatalyst in which the reduced metal is supported on the surface of the oxynitride as a promoter is obtained. Thereafter, the metal surface is naturally oxidized to form a metal oxide layer. That is, the photocatalyst obtained by the method for producing a photocatalyst according to the present invention includes a promoter having a core-shell structure (core: metal, shell: metal oxide) of a metal oxide and a metal on the surface of the oxynitride. It can be said that it is supported (see, for example, FIG. 1). Such a photocatalyst has a photocatalytic activity equal to or higher than that when a noble metal is supported as a promoter.
以上の通り、本発明によれば、資源が豊富で比較的安価な材料より製造される光触媒用助触媒を有するとともに、貴金属助触媒を担持した場合と同等以上の水分解活性を示す光触媒およびその製造方法を提供することができる。 As described above, according to the present invention, a photocatalyst having a photocatalyst cocatalyst produced from a resource-rich and relatively inexpensive material and having a water splitting activity equal to or higher than that of a noble metal cocatalyst supported thereon and the photocatalyst A manufacturing method can be provided.
以下、実施例により本発明をさらに具体的に説明するが、本発明は、その要旨を超えない限り、以下の実施例により制限されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not restrict | limited by a following example, unless the summary is exceeded.
＜光触媒の調製＞
（酸窒化物１の調製）
文献（Ｊｏｕｒｎａｌ ｏｆ Ｆｌｕｘ Ｇｒｏｕｗｔｈ，２０１０，５，８１／Ｊ.Ａｍ．Ｃｅｒａｍ．Ｓｏｃ ９９１，７４，２８７６）に記載の方法に従ってＬａＴｉＯ２Ｎを調製した。具体的には以下の通りである。
Ｌａ２Ｏ３（関東化学社製、９９．９９％）とＴｉＯ２（Ｓｉｇｍａ−Ａｌｄｒｉｃｈ社製、９９．９９％）とをモル比１：２でエタノールを用いて湿式混合し、これにフラックスであるＮａＣｌ（和光純薬工業社製、９９．５％）とＫＣｌ（和光純薬工業社製、９９．５％）との混合物（モル比１：１）を（Ｌａ＋Ｔｉ）：（Ｎａ＋Ｋ）＝１：２のモル比で加えた。これをアルミナ坩堝に入れ、１４２３Ｋまで１０Ｋ／ｍｉｎで加熱し、同温度で５時間保持した。その後１０２３Ｋまで１Ｋ／ｍｉｎで冷却し、さらに室温まで自然冷却した。取り出した試料を蒸留水で洗浄、濾過することによってフラックスを除去後、乾燥することで前駆体となるＬａ２Ｔｉ２Ｏ７を得た。次にこの前駆体を２００ｍＬ／ｍｉｎのＮＨ３気流下、１２２３Ｋで１５時間窒化し、ＬａＴｉＯ２Ｎを得た。ＸＲＤにより単相のＬａＴｉＯ２Ｎの生成が確認された。
<Preparation of photocatalyst>
(Preparation of oxynitride 1)
LaTiO 2 N was prepared according to the method described in the literature (Journal of Flux Group, 2010, 5, 81 / J. Am. Ceram. Soc 991, 74, 2876). Specifically, it is as follows.
La 2 O 3 (manufactured by Kanto Chemical Co., 99.99%) and TiO 2 (manufactured by Sigma-Aldrich, 99.99%) are wet-mixed with ethanol at a molar ratio of 1: 2, and this is mixed with flux. A mixture of a certain NaCl (manufactured by Wako Pure Chemical Industries, 99.5%) and KCl (manufactured by Wako Pure Chemical Industries, 99.5%) (molar ratio 1: 1) is (La + Ti) :( Na + K) = 1. : The molar ratio was 2. This was put into an alumina crucible, heated to 1423K at 10 K / min, and kept at the same temperature for 5 hours. Thereafter, it was cooled to 1023 K at 1 K / min, and further naturally cooled to room temperature. The sample taken out was washed with distilled water and filtered to remove the flux, followed by drying to obtain La 2 Ti 2 O 7 as a precursor. Next, this precursor was nitrided at 1223 K for 15 hours under a NH 3 stream of 200 mL / min to obtain LaTiO 2 N. XRD confirmed the formation of single-phase LaTiO 2 N.
（酸窒化物２の調製）
Ｌａ２Ｏ３とＴｉＯ２とをモル比１：２でエタノールを用いて湿式混合し、これにフラックスであるＮａＣｌを（Ｌａ＋Ｔｉ）：（Ｎａ）＝１：１０のモル比で加えた。それ以降の処理については、酸窒化物１の調製と同様の手順とし、ＬａＴｉＯ２Ｎを得た。ＸＲＤにより単相のＬａＴｉＯ２Ｎの生成が確認された。
(Preparation of oxynitride 2)
La 2 O 3 and TiO 2 and a molar ratio of 1: 2 with ethanol were wet-mixed, to which the NaCl is flux (La + Ti) :( Na) = 1: was added at 10 molar ratio. For subsequent processing, the same procedure as preparation of oxynitride 1, to obtain a
（酸窒化物３の調製）
文献（Ｊ．Ｐｈｙｓ．Ｃｈｅｍ．Ａ ２００２，１０６，６７５０）に記載の方法に従ってＬａＴｉＯ２Ｎを調製した。具体的には以下の通りである。
チタンテトライソプロポキシド（０．０２ｍｏｌ、関東化学社製、９７．０％）を室温でエチレングリコール（０．２ｍｏｌ、関東化学社製、９９．５％）に溶解した後、無水クエン酸（０．３ｍｏｌ、和光純薬工業社製、９８．０％）を添加し、３３３Ｋで加熱して完全に溶解させた。続いてこれにＬａ（ＮＯ３）３・６Ｈ２Ｏ（０．００２ｍｏｌ、関東化学社製、９９％）と２０ｍＬのメタノールとを添加し、４２３Ｋで透明なゲルが生成するまで加熱撹拌した。得られたポリマーゲルを５２３〜６２３Ｋで１時間熱分解して炭化させた後、空気中、７７３Ｋで１２時間焼成し、前駆体Ｌａ２Ｔｉ２Ｏ７を得た。この前駆体０．７ｇを２００ｍＬ／ｍｉｎのＮＨ３気流下、１２２３Ｋで１５時間窒化し、ＬａＴｉＯ２Ｎを得た。ＸＲＤにより単相のＬａＴｉＯ２Ｎの生成が確認された。
(Preparation of oxynitride 3)
LaTiO 2 N was prepared according to the method described in the literature (J. Phys. Chem. A 2002, 106, 6750). Specifically, it is as follows.
Titanium tetraisopropoxide (0.02 mol, manufactured by Kanto Chemical Co., Ltd., 97.0%) was dissolved in ethylene glycol (0.2 mol, manufactured by Kanto Chemical Co., Ltd., 99.5%) at room temperature, and then citric anhydride (0 3 mol, manufactured by Wako Pure Chemical Industries, Ltd., 98.0%) was added and heated at 333 K to be completely dissolved. Then this La (NO 3) 3 · 6H 2 O (0.002mol, Kanto Chemical Co., 99%) was added and methanol and 20 mL, was stirred and heated until a clear gel is produced at 423 K. The obtained polymer gel was pyrolyzed at 523-623K for 1 hour to be carbonized and then calcined in air at 773K for 12 hours to obtain a precursor La 2 Ti 2 O 7 . 0.7 g of this precursor was nitrided at 1223 K for 15 hours under a NH 3 stream of 200 mL / min to obtain LaTiO 2 N. XRD confirmed the formation of single-phase LaTiO 2 N.
（酸窒化物４の調製）
文献（Ｃａｔａｌｙｓｉｓ Ｔｏｄａｙ，２００３，７８，５５５−５６０）に記載の方法に従いＴａ２Ｏ５（高純度化学製、９９．９％）を２０ｍＬ／ｍｉｎのＮＨ３気流下、１１２３Ｋで１５時間窒化することによりＴａＯＮを得た。
(Preparation of oxynitride 4)
Nitriding Ta 2 O 5 (manufactured by High-Purity Chemical, 99.9%) under a flow of NH 3 at 20 mL / min for 15 hours at 1123 K in accordance with the method described in the literature (Catalysis Today, 2003, 78, 555-560) To obtain TaON.
（酸窒化物５の調製）
ＳｒＮｂＯ２Ｎを文献（ＣｈｅｍＳｕｓＣｈｅｍ．２０１１，４，７４−７８）に記載の方法に従って調製した。具体的には以下の通りである。
ＮｂＣｌ５（２１ｍｍｏｌ、高純度化学製、９９．９％）、無水クエン酸（２１０ｍｍｏｌ、和光純薬工業社製、９８．０％）、エチレングリコール（８４０ｍｍｏｌ、関東化学社製、９９．５％）、ＳｒＣＯ３（２１ｍｍｏｌ、関東化学社製、９９．５％）をメタノール１００ｍＬに溶解し、４７３Ｋで１晩加熱してゲル化させた。得られたポリマーゲルを６２３Ｋで熱分解させた後、空気中、９７３Ｋで２時間焼成し、粉砕した後さらに９７３〜１１２３Ｋで２時間焼成してＳｒ-Ｎｂ複合酸化物を得た。得られた複合酸化物を２５０ｍＬ／ｍｉｎのＮＨ３気流下、１０２３〜１２２３Ｋで１５時間窒化し、ＳｒＮｂＯ２Ｎを得た。
(Preparation of oxynitride 5)
SrNbO 2 N was prepared according to the method described in the literature (ChemSusChem. 2011, 4, 74-78). Specifically, it is as follows.
NbCl 5 (21 mmol, high-purity chemical, 99.9%), citric anhydride (210 mmol, Wako Pure Chemical Industries, 98.0%), ethylene glycol (840 mmol, manufactured by Kanto Chemical Co., 99.5%) , SrCO 3 (21 mmol, manufactured by Kanto Chemical Co., Inc., 99.5%) was dissolved in 100 mL of methanol and heated at 473 K overnight to cause gelation. The obtained polymer gel was thermally decomposed at 623K, calcined in air at 973K for 2 hours, pulverized, and further calcined at 973-1123K for 2 hours to obtain a Sr—Nb composite oxide. The obtained composite oxide was nitrided at 1023 to 1223K for 15 hours under a flow of NH 3 at 250 mL / min to obtain SrNbO 2 N.
（実施例１：（ＣｏＯｘ／Ｃｏ）／酸窒化物１）
得られた酸窒化物１（０．３ｇ）を、Ｃｏ（ＮＯ３）２・６Ｈ２Ｏ（ＬａＴｉＯ２Ｎを基準として２．０質量％のＣｏ）を含む水溶液（３ｍＬ）に懸濁し、蒸発皿内、ウォーターバス上でガラス棒により攪拌しながら溶媒を蒸発乾燥させた。
(Example 1: (CoO x / Co) / oxynitride 1)
The obtained oxynitride 1 (0.3 g) was suspended in an aqueous solution (3 mL) containing Co (NO 3 ) 2 .6H 2 O (2.0 mass% Co based on LaTiO 2 N) and evaporated. The solvent was evaporated to dryness while stirring with a glass rod in a dish on a water bath.
得られたＣｏ（ＮＯ３）２／酸窒化物１を、２００ｍＬ／ｍｉｎのＮＨ３気流下で、７７３〜１０７３Ｋで１時間還元処理した後、室温まで冷却して、酸窒化物１にＣｏＯｘおよびＣｏを担持した光触媒「（ＣｏＯｘ／Ｃｏ）／酸窒化物１」を得た。なお、ＣｏＯｘとは、ＣｏＯ、Ｃｏ２Ｏ３、Ｃｏ３Ｏ４等のコバルト酸化物の混合物を意味する。 The resulting Co (NO 3) 2 / oxynitride 1, with NH 3 stream of 200 mL / min, after 1 hour reduced at 773～1073K, and cooled to room temperature, the oxynitride 1 CoO x And the photocatalyst “(CoO x / Co) / oxynitride 1” supporting Co was obtained. CoO x means a mixture of cobalt oxides such as CoO, Co 2 O 3 , and Co 3 O 4 .
（実施例２：（ＣｏＯｘ／Ｃｏ）／酸窒化物３）
酸窒化物として酸窒化物３を使用したほかは、実施例１に記載の調製方法と同様の手順で、酸窒化物３にＣｏＯｘおよびＣｏを担持した光触媒「（ＣｏＯｘ／Ｃｏ）／酸窒化物３」を得た。
(Example 2: (CoO x / Co) / oxynitride 3)
The photocatalyst “(CoO x / Co) / acid in which CoO x and Co are supported on oxynitride 3 in the same procedure as the preparation method described in Example 1 except that oxynitride 3 was used as the oxynitride. Nitride 3 ”was obtained.
（実施例３：（ＣｏＯｘ／Ｃｏ）／酸窒化物２）
酸窒化物として酸窒化物２を使用したほかは、実施例１に記載の調製方法と同様の手順で、酸窒化物２にＣｏＯｘおよびＣｏを担持した光触媒「（ＣｏＯｘ／Ｃｏ）／酸窒化物２」を得た。
(Example 3: (CoO x / Co) / oxynitride 2)
The photocatalyst “(CoO x / Co) / acid in which CoO x and Co are supported on
（実施例４：（ＭｎＯｘ／Ｍｎ）／酸窒化物２）
酸窒化物２（０．３ｇ）をＭｎＣｌ２（ＬａＴｉＯ２Ｎに対して１．９質量％のＭｎ）を含む水溶液（３ｍＬ）に添加し、蒸発皿内、ウォーターバス上でガラス棒により攪拌しながら溶媒を蒸発乾燥させた。その後、空気中、４７３Ｋで焼成することによって、ＭｎＯｘを酸窒化物２に担持してなる「ＭｎＯｘ／酸窒化物２」を得た。なお、ＭｎＯｘとは、ＭｎＯ、ＭｎＯ２、Ｍｎ２Ｏ３、Ｍｎ３Ｏ４等のマンガン酸化物の混合物を意味する。
(Example 4: (MnO x / Mn) / oxynitride 2)
Oxynitride 2 (0.3 g) was added to an aqueous solution (3 mL) containing MnCl 2 (1.9% by mass of Mn with respect to LaTiO 2 N) and stirred with a glass rod in an evaporating dish on a water bath. The solvent was evaporated to dryness. Then, “MnO x /
得られたＭｎＯｘ／酸窒化物２を、２００ｍＬ／ｍｉｎのＮＨ３気流下で、９２３Ｋで１時間還元処理した後、室温まで冷却して、酸窒化物２にＭｎＯｘおよびＭｎを担持した光触媒「（ＭｎＯｘ／Ｍｎ）／酸窒化物２」を得た。
The obtained MnO x /
（実施例５：（ＮｉＯｘ／Ｎｉ）／酸窒化物２）
酸窒化物２（０．３ｇ）をＮｉ（ＮＯ３）２・６Ｈ２Ｏ（ＬａＴｉＯ２Ｎに対して２質量％のＮｉ）を含む水溶液（３ｍＬ）に添加し、蒸発皿内、ウォーターバス上でガラス棒により攪拌しながら溶媒を蒸発乾燥させた。その後、空気中、４７３Ｋで焼成することによって、ＮｉＯｘを酸窒化物２に担持してなる「ＮｉＯｘ／酸窒化物２」を得た。なお、ＮｉＯｘとは、ＮｉＯ、Ｎｉ２Ｏ３等のニッケル酸化物の混合物を意味する。
(Example 5: (NiO x / Ni) / oxynitride 2)
Oxynitride 2 (0.3 g) is added to an aqueous solution (3 mL) containing Ni (NO 3 ) 2 .6H 2 O (2% by mass of Ni with respect to LaTiO 2 N), and in an evaporating dish on a water bath The solvent was evaporated to dryness while stirring with a glass rod. Thereafter, in the air, by baking at 473 K, to obtain a formed by carrying NiO x to
得られたＮｉＯｘ／酸窒化物２を、２００ｍＬ／ｍｉｎのＮＨ３気流下で、９２３Ｋで１時間還元処理した後、室温まで冷却して、酸窒化物２にＮｉＯｘおよびＮｉを担持した光触媒「（ＮｉＯｘ／Ｎｉ）／酸窒化物２」を得た。
The obtained NiO x /
（比較例１：ＣｏＯｘ／酸窒化物１）
酸窒化物１を空気中、４７３Ｋで２時間焼成した。焼成後の酸窒化物１（０．３ｇ）を、Ｃｏ（ＮＯ３）２・６Ｈ２Ｏ（ＬａＴｉＯ２Ｎを基準として２．０質量％のＣｏ）を含む水溶液（３ｍＬ）に懸濁し、蒸発皿内、ウォーターバス上でガラス棒により攪拌しながら溶媒を蒸発乾燥させた。その後、空気中、４７３Ｋで焼成することによって、ＣｏＯｘを酸窒化物１に担持してなる「ＣｏＯｘ／酸窒化物１」を得た。
(Comparative Example 1: CoO x / oxynitride 1)
Oxynitride 1 was calcined in air at 473K for 2 hours. The oxynitride 1 (0.3 g) after firing is suspended in an aqueous solution (3 mL) containing Co (NO 3 ) 2 .6H 2 O (2.0 mass% Co based on LaTiO 2 N) and evaporated. The solvent was evaporated to dryness while stirring with a glass rod in a dish on a water bath. Thereafter, in the air, by baking at 473 K, to obtain a formed by carrying CoO x the oxynitride 1 "CoO x / oxynitride 1".
（比較例２：ＩｒＯ２／酸窒化物１）
文献（Ｊ．Ｐｈｙｓ．Ｃｈｅｍ．Ａ２００２，１０６，６５７０）に記載の方法に従ってＩｒＯ２コロイド溶液を調整した。具体的には以下の通りである。
Ｎａ２［ＩｒＣｌ６］・６Ｈ２Ｏ（０．１５９ｇ）を、１００ｍＬの蒸留水中に溶解させ、ｐＨを５Ｍ ＮａＯＨで１２．０に調整した。この溶液を３５３Ｋのウォーターバス中で加熱し、無色透明の溶液を得た。この溶液を室温まで冷却し、ＨＮＯ３水溶液でｐＨ８．５〜９．５に調整した後、再び３５３Ｋで加熱して濃青色のＩｒＯ２コロイド溶液を得た。
(Comparative Example 2: IrO 2 / oxynitride 1)
An IrO 2 colloid solution was prepared according to the method described in the literature (J. Phys. Chem. A 2002, 106, 6570). Specifically, it is as follows.
Na 2 [IrCl 6 ] · 6H 2 O (0.159 g) was dissolved in 100 mL of distilled water and the pH was adjusted to 12.0 with 5M NaOH. This solution was heated in a 353 K water bath to obtain a colorless and transparent solution. This solution was cooled to room temperature, adjusted to pH 8.5 to 9.5 with HNO 3 aqueous solution, and then heated again at 353 K to obtain a dark blue IrO 2 colloid solution.
酸窒化物１（０．３ｇ）をＩｒＯ２コロイド溶液（ＬａＴｉＯ２Ｎに対して２．０質量％のＩｒＯ２、ＮａＯＨ水溶液を用いてｐＨを５．０に調整）２００ｍＬ中で１時間攪拌してＩｒＯ２を酸窒化物１に吸着させ、濾別または蒸発乾固した後、空気中、４７３Ｋで１時間焼成することによって、ＩｒＯ２を酸窒化物１に担持してなる光触媒「ＩｒＯ２／酸窒化物１」を得た。 Oxynitride 1 (0.3 g) was stirred in 200 mL of IrO 2 colloid solution (2.0 mass% IrO 2 with respect to LaTiO 2 N, pH adjusted to 5.0 using NaOH aqueous solution) for 1 hour. IrO 2 is adsorbed on oxynitride 1 and filtered or evaporated to dryness, and then calcined in air at 473 K for 1 hour, whereby IrO 2 is supported on oxynitride 1 to form a photocatalyst “IrO 2 / Oxynitride 1 "was obtained.
（比較例３：ＩｒＯ２／酸窒化物３）
酸窒化物として酸窒化物３を使用したほかは、比較例２に記載の調製方法と同様の手順で、ＩｒＯ２を酸窒化物３に担持してなる光触媒「ＩｒＯ２／酸窒化物３」を得た。
(Comparative Example 3: IrO 2 / oxynitride 3)
A photocatalyst “IrO 2 / oxynitride 3” obtained by supporting IrO 2 on oxynitride 3 in the same procedure as the preparation method described in Comparative Example 2, except that oxynitride 3 was used as the oxynitride. Got.
（比較例４：ＭｎＯｘ／酸窒化物１）
酸窒化物１（０．３ｇ）をＭｎＣｌ２（ＬａＴｉＯ２Ｎに対して２質量％のＭｎ）を含む水溶液（３ｍＬ）に添加し、蒸発皿内、ウォーターバス上でガラス棒により攪拌しながら溶媒を蒸発乾燥させた。その後、空気中、４７３Ｋで焼成することによって、ＭｎＯｘを酸窒化物１に担持してなる「ＭｎＯｘ／酸窒化物１」を得た。
(Comparative Example 4: MnO x / oxynitride 1)
Oxynitride 1 (0.3 g) was added to an aqueous solution (3 mL) containing MnCl 2 ( 2 % by mass of Mn with respect to LaTiO 2 N), and a solvent was stirred in a water bath on a water bath while stirring with a glass rod. Was evaporated to dryness. Then, “MnO x / oxynitride 1” obtained by supporting MnO x on oxynitride 1 was obtained by firing at 473 K in air.
（比較例５：ＮｉＯｘ／酸窒化物１）
酸窒化物１（０．３ｇ）をＮｉ（ＮＯ３）２・６Ｈ２Ｏ（ＬａＴｉＯ２Ｎに対して２質量％のＮｉ）を含む水溶液（３ｍＬ）に添加し、蒸発皿内、ウォーターバス上でガラス棒により攪拌しながら溶媒を蒸発乾燥させた。その後、空気中、４７３Ｋで焼成することによって、ＮｉＯｘを酸窒化物１に担持してなる「ＮｉＯｘ／酸窒化物１」を得た。
(Comparative Example 5: NiO x / oxynitride 1)
Oxynitride 1 (0.3 g) is added to an aqueous solution (3 mL) containing Ni (NO 3 ) 2 .6H 2 O (2% by mass of Ni with respect to LaTiO 2 N), and then in an evaporating dish on a water bath The solvent was evaporated to dryness while stirring with a glass rod. Thereafter, in the air, by baking at 473 K, to obtain a formed by carrying NiO x to oxynitride 1 "NiO x / oxynitride 1".
（比較例６：（ＣｏＯｘ／Ｃｏ）／酸窒化物４)
酸窒化物として酸窒化物４を使用したほかは、実施例１に記載の調製方法と同様の手順で、酸窒化物４にＣｏＯｘおよびＣｏを担持した光触媒「（ＣｏＯｘ／Ｃｏ）／酸窒化物４」を得た。
(Comparative Example 6: (CoO x / Co) / oxynitride 4)
The photocatalyst “(CoO x / Co) / acid in which CoO x and Co are supported on oxynitride 4 in the same procedure as the preparation method described in Example 1, except that oxynitride 4 was used as the oxynitride. Nitride 4 ”was obtained.
（比較例７：助触媒無担持酸窒化物４）
酸窒化物４に助触媒を担持せずそのままの状態で光触媒活性を評価した。
(Comparative Example 7: Cocatalyst unsupported oxynitride 4)
The photocatalytic activity was evaluated in the state where the oxynitride 4 did not carry a promoter.
＜光触媒電極の調製＞
調製した酸窒化物５の光触媒電極を以下のように調製した。
アセトン４５ｍｌにヨウ素９ｍｇを溶解し、調製した酸窒化物５（３６ｍｇ）を懸濁させて１５分間超音波処理を行った。得られた懸濁液に、２枚のＴｉ板を浸し、１００Ｖの電圧を２０秒間印加して酸窒化物が吸着した「酸窒化物５／Ｔｉ」を調製した。これに１０ｍＭ ＮｂＣｌ５メタノール溶液２５μＬを滴下し、空気中で乾燥させる操作を６回繰り返したのち、１００ｍＬ／ｍｉｎのＮＨ３気流下、７５３Ｋで３０分間加熱してポストネッキング処理された「酸窒化物５／Ｔｉ」を得た。光触媒電極面積は２〜３ｃｍ２であった。
<Preparation of photocatalytic electrode>
The prepared oxynitride 5 photocatalytic electrode was prepared as follows.
9 mg of iodine was dissolved in 45 ml of acetone, and the prepared oxynitride 5 (36 mg) was suspended and subjected to ultrasonic treatment for 15 minutes. Two Ti plates were immersed in the obtained suspension, and a voltage of 100 V was applied for 20 seconds to prepare “oxynitride 5 / Ti” in which oxynitride was adsorbed. To this, 25 μL of 10 mM NbCl 5 methanol solution was added dropwise and dried in air six times, and then heated at 753 K for 30 minutes in a NH 3 stream of 100 mL / min, and “oxynitride treated by post-necking” 5 / Ti "was obtained. The photocatalytic electrode area was 2-3 cm 2 .
（実施例６：（ＣｏＯｘ／Ｃｏ）／酸窒化物５／Ｔｉ電極）
酸窒化物５／ＴｉにＣｏ（ＮＯ３）２・６Ｈ２Ｏ（ＳｒＮｂＯ２Ｎを基準として２．０質量％のＣｏ）を含む水溶液を滴下し、空気中で乾燥させた。そののち１００ｍＬ／ｍｉｎのＮＨ３気流下、８４８Ｋで３０分間加熱して（ＣｏＯｘ／Ｃｏ）／酸窒化物５／Ｔｉ電極を得た。
(Example 6: (CoO x / Co) / oxynitride 5 / Ti electrode)
An aqueous solution containing Co (NO 3 ) 2 .6H 2 O (2.0 mass% Co based on SrNbO 2 N) was added dropwise to oxynitride 5 / Ti and dried in air. After that, heating was performed at 848 K for 30 minutes under an NH 3 stream of 100 mL / min to obtain a (CoO x / Co) / oxynitride 5 / Ti electrode.
（比較例８：ＣｏＯｘ／酸窒化物５／Ｔｉ電極）
酸窒化物５／ＴｉにＣｏ（ＮＯ３）２・６Ｈ２Ｏ（ＳｒＮｂＯ２Ｎを基準として２．０質量％のＣｏ）を含む水溶液を滴下し、空気中で乾燥させた。その後、空気中、４２３Ｋで１時間焼成することによって、ＣｏＯｘ／酸窒化物５／Ｔｉ電極を得た。
(Comparative Example 8: CoO x / oxynitride 5 / Ti electrode)
An aqueous solution containing Co (NO 3 ) 2 .6H 2 O (2.0 mass% Co based on SrNbO 2 N) was added dropwise to oxynitride 5 / Ti and dried in air. Thereafter, in the air, followed by firing for 1 hour at 423 K, to obtain a CoO x / oxynitride 5 / Ti electrode.
（比較例９：ＩｒＯ２／酸窒化物５／Ｔｉ電極）
酸窒化物５／Ｔｉを前記ＩｒＯ２コロイド溶液（１５体積％）に一晩浸漬し、ＩｒＯ２／酸窒化物５／Ｔｉ電極を得た。
(Comparative Example 9: IrO 2 / oxynitride 5 / Ti electrode)
It said oxynitride 5 / Ti IrO 2 colloid solution (15 vol%) was immersed overnight to give the IrO 2 / oxynitride 5 / Ti electrode.
＜光水分解反応評価（１）：粉末光触媒による活性評価＞
調製した光触媒の活性は、犠牲試薬（Ａｇ＋）存在下の光水分解反応における酸素生成速度の比較により評価した。具体的には以下の通りである。
光水分解反応は、図２に示すような真空排気用ポンプ、循環ポンプ、光触媒および水を入れるセル、気体採取バルブ、ならびにガスクロマトグラフ分析装置（ＧＣ）を備えた閉鎖系の反応装置で評価した。光源は３００Ｗのキセノンランプおよびカットオフフィルター（λ＞４２０ｎｍ）を使用し、温度上昇を避けるためランプとセルとの間にはウォータージャケットを設け冷却した。評価の際は、光触媒０．１ｇまたは０．２ｇを、０．０２Ｍ ＡｇＮＯ３（２００ｍＬ、０．２ｇのＬａ２Ｏ３でｐＨを８．３に調整）溶液中に懸濁させ、あらかじめ反応装置内を数回脱気することで空気が残存しないことを確認した後に光照射を開始し、ガスクロマトグラフィーにより気体（酸素）の生成量を測定した。結果を下記表１に示す。なお、酸素生成速度は、観測された酸素生成速度(μｍｏｌ／ｈ)と触媒重量あたりの酸素生成速度（μｍｏｌ／ｈｇｃａｔ）との両方を示した。
<Photo water splitting reaction evaluation (1): Activity evaluation by powder photocatalyst>
The activity of the prepared photocatalyst was evaluated by comparing the oxygen production rate in the photohydrolysis reaction in the presence of the sacrificial reagent (Ag + ). Specifically, it is as follows.
The photo-water splitting reaction was evaluated with a closed reactor equipped with a vacuum exhaust pump, a circulation pump, a photocatalyst and water cell, a gas sampling valve, and a gas chromatograph analyzer (GC) as shown in FIG. . A 300 W xenon lamp and a cut-off filter (λ> 420 nm) were used as the light source, and a water jacket was provided between the lamp and the cell in order to avoid a temperature rise and cooling was performed. In the evaluation, 0.1 g or 0.2 g of the photocatalyst was suspended in a 0.02M AgNO 3 (200 mL, 0.2 g La 2 O 3 to adjust the pH to 8.3) solution, and the reaction apparatus was used in advance. After confirming that no air remained by degassing the interior several times, light irradiation was started, and the amount of gas (oxygen) produced was measured by gas chromatography. The results are shown in Table 1 below. The oxygen production rate showed both the observed oxygen production rate (μmol / h) and the oxygen production rate per catalyst weight (μmol / hg cat ).
＜光水分解反応評価（２）：光触媒電極による活性評価＞
調製した光触媒電極の性能は、ポテンショスタットを用いた３電極系での電流−電位測定によって行った（図３）。平面窓付きのパイレックスガラス製電気化学セルを用い、参照極にＡｇ／ＡｇＣｌ電極、対極にＰｔワイヤーを用いた。電解液にはＮａ２ＳＯ４０．１Ｍ水溶液（ｐＨ＝５．９）を用いた。電気化学セル内部はアルゴンで満たし、かつ、測定前に十分にバブリングを行うことによって溶存する酸素、二酸化炭素を除去した。光電気化学測定には、コールドミラーとカットオフフィルター（ＨＯＹＡ社製、Ｌ−４２）を装着した３００Ｗキセノンランプを光源として用い、電気化学セルの平面窓から波長４２０ｎｍ以上の白色光を照射した。それぞれの電極について、測定電位０Ｖ、０．５Ｖ、１．０Ｖ（ｖｓ． ＲＨＥ）における光電流密度（ｍＡ／ｃｍ２）を測定した。結果を下記表２に示す。
<Photo water splitting reaction evaluation (2): Activity evaluation by photocatalytic electrode>
The performance of the prepared photocatalytic electrode was measured by current-potential measurement in a three-electrode system using a potentiostat (FIG. 3). A Pyrex glass electrochemical cell with a flat window was used, an Ag / AgCl electrode was used for the reference electrode, and a Pt wire was used for the counter electrode. A Na 2 SO 4 0.1M aqueous solution (pH = 5.9) was used as the electrolytic solution. The inside of the electrochemical cell was filled with argon, and dissolved oxygen and carbon dioxide were removed by sufficiently bubbling before measurement. For the photoelectrochemical measurement, a 300 W xenon lamp equipped with a cold mirror and a cut-off filter (manufactured by HOYA, L-42) was used as a light source, and white light having a wavelength of 420 nm or more was irradiated from a planar window of the electrochemical cell. About each electrode, the photocurrent density (mA / cm < 2 >) in the measurement electric potential 0V, 0.5V, 1.0V (vs. RHE) was measured. The results are shown in Table 2 below.
表１に示す結果から明らかなように、酸窒化物１を用いた場合においては、助触媒としてＩｒＯ２を担持した光触媒（比較例２）と比較して、助触媒としてＣｏＯｘを担持した光触媒（比較例１）であっても酸素生成活性が同等以上であったが、Ｃｏ（ＮＯ３）２を担持したのち還元処理を実施する本発明に係る光触媒（実施例１）にあっては、それよりもさらに光触媒活性を向上させることができた。また酸化物１と同じくフラックス法にて調製した酸化物２を用いた場合でも、Ｃｏ（ＮＯ３）２を担持したのち還元処理を実施した場合には、ＩｒＯ２よりも高い酸素生成活性を示した（実施例３）。
As is apparent from the results shown in Table 1, in the case of using oxynitride 1, the photocatalyst carrying CoO x as the cocatalyst was compared with the photocatalyst carrying IrO 2 as the cocatalyst (Comparative Example 2). Even in (Comparative Example 1), the oxygen generation activity was equal to or higher than that, but in the photocatalyst (Example 1) according to the present invention in which the reduction treatment is performed after supporting Co (NO 3 ) 2 , The photocatalytic activity could be further improved. Even when the
これは錯体重合法により得られた酸窒化物３を用いた場合も同様であり、Ｃｏ（ＮＯ３）２を担持したのち還元処理してなる助触媒を有する光触媒（実施例２）は、ＩｒＯ２を担持した光触媒（比較例３）と比較して、酸素生成活性が著しく向上していた。
The same applies to the case of using the oxynitride 3 obtained by the complex polymerization method, and the photocatalyst (Example 2) having a cocatalyst formed by carrying Co (NO 3 ) 2 and then carrying out reduction treatment is
また、比較例４、５のようにＭｎＯｘ、ＮｉＯｘを担持した場合には還元処理を実施しないと酸素生成速度はＩｒＯ２（比較例２）に比較して１／１０程度の低い値であったが、実施例４〜５から明らかなように、各種金属酸化物を還元処理してなる助触媒が担持された光触媒とすることで、比較的高い酸素生成活性を示した。これらの結果から、単に酸化物を担持するのではなく、これらを高温で還元処理することによって酸素生成反応が促進されることが明らかである。 In addition, when MnO x and NiO x are supported as in Comparative Examples 4 and 5, if the reduction treatment is not performed, the oxygen generation rate is a low value of about 1/10 compared to IrO 2 (Comparative Example 2). However, as apparent from Examples 4 to 5, a relatively high oxygen generation activity was exhibited by using a photocatalyst on which a cocatalyst formed by reducing various metal oxides was supported. From these results, it is clear that the oxygen generation reaction is promoted by reducing them at a high temperature rather than simply supporting oxides.
また表２に示す結果から明らかなように、この傾向は光触媒電極で評価した場合も同様であった。すなわち、Ｃｏ（ＮＯ３）２を担持したのち還元処理を実施する光触媒電極（実施例６）は、ＣｏＯｘを担持した光触媒電極（比較例８）およびＩｒＯ２を担持した光触媒電極（比較例９）と比較して、光電流密度が著しく向上していた。 As is clear from the results shown in Table 2, this tendency was the same when evaluated with the photocatalytic electrode. That is, the photocatalyst electrode (Example 6) that carries Co (NO 3 ) 2 and then performs the reduction treatment is the photocatalyst electrode that carries CoO x (Comparative Example 8) and the photocatalyst electrode that carries IrO 2 (Comparative Example 9). ) Significantly improved the photocurrent density.
一方、ＴａＯＮに助触媒ＩｒＯ２を担持すると酸素生成速度が向上することは公知（Ｃｈｅｍｉｓｔｒｙ Ｌｅｔｔｅｒｓ，２００８，３７，１３８−１３９やＥｎｅｒｇｙ Ｅｎｖｉｒｏｎ．Ｓｃｉ．，２０１１，４，４１３８−４１４７）であるにもかかわらず、表１に示す結果から明らかなように、比較例６、７のように酸窒化物がＴａＯＮである場合には、Ｃｏ（ＮＯ３）２を担持したのち還元処理を実施すると、助触媒を担持しない場合に比較して大幅に酸素生成速度が低下した。このことから、本技術に適用する酸窒化物はチタン系酸窒化物およびニオブ系酸窒化物が好適であることがわかった。 On the other hand, it is publicly known (Chemistry Letters, 2008, 37, 138-139 and Energy Environ. Sci., 2011, 4, 4138-4147) that TaON supports co-catalyst IrO 2 . Regardless, as is apparent from the results shown in Table 1, when the oxynitride is TaON as in Comparative Examples 6 and 7, when the reduction treatment is performed after Co (NO 3 ) 2 is supported, Compared with the case where no catalyst was supported, the oxygen generation rate was significantly reduced. From this, it was found that titanium oxynitride and niobium oxynitride are suitable as the oxynitride applied to the present technology.
＜ＸＰＳによる構造解析＞
助触媒担持量を１５質量％とした以外は実施例１と同様にして光触媒を調製し、得られた光触媒の構造をＸＰＳにより解析した。結果を図４に示す。
<Structural analysis by XPS>
A photocatalyst was prepared in the same manner as in Example 1 except that the amount of promoter supported was 15% by mass, and the structure of the obtained photocatalyst was analyzed by XPS. The results are shown in FIG.
図４に示すように、還元処理してなる助触媒の表面を解析したところＣｏ２＋に由来するピークが観測された（ｏｒｉｇｉｎａｌ）。これは、助触媒表面にコバルト酸化物（ＣｏＯ）が存在していることを示唆している。また、エッチング時間１０秒で、金属Ｃｏ由来のピークが観測され（１０ｓ）、エッチング時間が長くなるにつれてＣｏ２＋に由来するピークが徐々に消失した（２０ｓ〜６０ｓ）。この結果から、助触媒は表面が酸化物層で覆われているが、酸化物層の下層に金属Ｃｏが存在していることが示唆された。すなわち、本発明に係る光触媒においては、助触媒が金属酸化物と金属とのコアシェル型構造（コア：金属、シェル：金属酸化物）をとっていることが示唆された。 As shown in FIG. 4, when the surface of the cocatalyst subjected to the reduction treatment was analyzed, a peak derived from Co 2+ was observed (original). This suggests that cobalt oxide (CoO) is present on the promoter surface. In addition, a peak derived from metal Co was observed at an etching time of 10 seconds (10 s), and the peak derived from Co 2+ gradually disappeared (20 s to 60 s) as the etching time increased. This result suggests that the surface of the promoter is covered with an oxide layer, but metal Co is present in the lower layer of the oxide layer. That is, in the photocatalyst according to the present invention, it was suggested that the promoter has a core-shell structure (core: metal, shell: metal oxide) of a metal oxide and a metal.
以上、現時点において、もっとも、実践的であり、かつ、好ましいと思われる実施形態に関連して本発明を説明したが、本発明は、本願明細書中に開示された実施形態に限定されるものではなく、請求の範囲および明細書全体から読み取れる発明の要旨或いは思想に反しない範囲で適宜変更可能であり、そのような変更を伴う光触媒およびその製造方法もまた本発明の技術的範囲に包含されるものとして理解されなければならない。 While the present invention has been described in connection with embodiments that are presently the most practical and preferred, the present invention is not limited to the embodiments disclosed herein. However, the present invention can be changed as appropriate without departing from the spirit or concept of the invention that can be read from the claims and the entire specification, and a photocatalyst and a method for producing the same are also included in the technical scope of the present invention. Must be understood.
本発明に係る光触媒は高い水分解活性を有し、太陽光を利用した水分解反応を行うことにより水素および／または酸素を製造する光水分解反応に特に好適に用いられる。 The photocatalyst according to the present invention has a high water splitting activity, and is particularly preferably used for a photowater splitting reaction that produces hydrogen and / or oxygen by performing a water splitting reaction using sunlight.
Claims (8)
Ｔｉおよび／またはＮｂを含む酸窒化物に、金属元素Ｍを含む化合物を担持させる第１の工程と、
前記金属元素Ｍを含む化合物を還元処理する第２の工程と、
を含むことを特徴とする、光触媒の製造方法。 A method for producing a photocatalyst obtained by supporting a metal oxide represented by MO x and a metal M as a cocatalyst on an oxynitride containing Ti and / or Nb,
A first step of supporting a compound containing a metal element M on an oxynitride containing Ti and / or Nb;
A second step of reducing the compound containing the metal element M;
The manufacturing method of the photocatalyst characterized by including these.
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