JP2015116535A - Catalyst for water-splitting reaction - Google Patents
Catalyst for water-splitting reaction Download PDFInfo
- Publication number
- JP2015116535A JP2015116535A JP2013261473A JP2013261473A JP2015116535A JP 2015116535 A JP2015116535 A JP 2015116535A JP 2013261473 A JP2013261473 A JP 2013261473A JP 2013261473 A JP2013261473 A JP 2013261473A JP 2015116535 A JP2015116535 A JP 2015116535A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- water
- cowo
- reaction
- splitting reaction
- 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
- 239000003054 catalyst Substances 0.000 title claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- OMAWWKIPXLIPDE-UHFFFAOYSA-N (ethyldiselanyl)ethane Chemical compound CC[Se][Se]CC OMAWWKIPXLIPDE-UHFFFAOYSA-N 0.000 claims description 12
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 3
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 abstract description 9
- 229910001930 tungsten oxide Inorganic materials 0.000 abstract description 8
- KLNIPFWTZXANST-UHFFFAOYSA-N cobalt(2+) dioxido(dioxo)tungsten Chemical compound [Co+2].[O-][W]([O-])(=O)=O KLNIPFWTZXANST-UHFFFAOYSA-N 0.000 abstract 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 27
- 239000001301 oxygen Substances 0.000 description 27
- 229910052760 oxygen Inorganic materials 0.000 description 27
- 239000000243 solution Substances 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000009616 inductively coupled plasma Methods 0.000 description 4
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 description 3
- 239000012327 Ruthenium complex Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000007809 chemical reaction catalyst Substances 0.000 description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- JLYXEDWXODCCMV-UHFFFAOYSA-K Cl(=O)(=O)(=O)[O-].N1=C(C=CC=C1)C1=NC=CC=C1.N1=C(C=CC=C1)C1=NC=CC=C1.N1=C(C=CC=C1)C1=NC=CC=C1.[Ru+3].Cl(=O)(=O)(=O)[O-].Cl(=O)(=O)(=O)[O-] Chemical compound Cl(=O)(=O)(=O)[O-].N1=C(C=CC=C1)C1=NC=CC=C1.N1=C(C=CC=C1)C1=NC=CC=C1.N1=C(C=CC=C1)C1=NC=CC=C1.[Ru+3].Cl(=O)(=O)(=O)[O-].Cl(=O)(=O)(=O)[O-] JLYXEDWXODCCMV-UHFFFAOYSA-K 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910001195 gallium oxide Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 239000006199 nebulizer Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 230000002165 photosensitisation Effects 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 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
Landscapes
- Catalysts (AREA)
Abstract
Description
本発明は、水の電気化学及び光化学電気分解用の触媒に関する。 The present invention relates to a catalyst for water electrochemistry and photochemical electrolysis.
水素は、クリーンな無公害化石燃料代替物であるため、理想的な燃料源であると長い間考えられてきた。１つの水素源は、下式（１）
（１） ２Ｈ2Ｏ→Ｏ2＋２Ｈ2
で示されるように、水素（Ｈ2）と酸素（Ｏ2）への水の分解である。
Hydrogen has long been considered an ideal fuel source because it is a clean, non-polluting fossil fuel alternative. One hydrogen source is represented by the following formula (1)
(1) 2H 2 O → O 2 + 2H 2
As shown, the decomposition of water into hydrogen (H 2 ) and oxygen (O 2 ).
電気化学的半電池において、水分解反応は２つの半反応を含んでいる。
（２） ２Ｈ2Ｏ→Ｏ2＋４Ｈ+＋４ｅ-
（３） ２Ｈ+＋２ｅ-→Ｈ2
そして日光を用いて水から製造された水素は、豊富な、再生可能な、クリーンエネルギー源を与える。そのため、水から水素を製造する有効な酸素発生反応反応（ＯＥＲ）触媒が研究されてきた。例えば光半導体に酸化反応助触媒と還元反応助触媒を担持した光水分解反応用触媒が提案され、具体的には、ロジウムを還元反応助触媒として用いられている（特許文献１参照）。しかしながら、ロジウムは希少な元素であり、高価であるため、その触媒を大スケールで用いることは実際的ではない。従って、代替燃料源としての水素の開発において、改良されたＯＥＲ触媒がとても有用である。
In an electrochemical half cell, the water splitting reaction involves two half reactions.
(2) 2H 2 O → O 2 + 4H + + 4e −
(3) 2H + + 2e − → H 2
And the hydrogen produced from water using sunlight provides a rich, renewable, and clean energy source. Therefore, effective oxygen evolution reaction (OER) catalysts for producing hydrogen from water have been studied. For example, a photo-water splitting reaction catalyst in which an oxidation reaction promoter and a reduction reaction promoter are supported on an optical semiconductor has been proposed. Specifically, rhodium is used as a reduction reaction promoter (see Patent Document 1). However, since rhodium is a rare element and expensive, it is not practical to use the catalyst on a large scale. Thus, improved OER catalysts are very useful in the development of hydrogen as an alternative fuel source.
そこでこの水分解反応用の触媒として、タングステン酸コバルト（ＣｏＷＯ4）を用いることが提案されている（特許文献２参照）。 Therefore, it has been proposed to use cobalt tungstate (CoWO 4 ) as a catalyst for this water splitting reaction (see Patent Document 2).
水分解反応用の触媒としてタングステン酸コバルトは、単独で用いた場合、水分解性は十分に高くないことが見いだされた。そこで本願発明は、より効果の高い水分解反応用の触媒を提供することを目的とする。 It has been found that cobalt tungstate is not sufficiently high when used alone as a catalyst for water splitting reaction. Therefore, an object of the present invention is to provide a more effective catalyst for water splitting reaction.
上記課題を解決するために本発明によれば、担体としての酸化タングステン（ＷＯ3）上にタングステン酸コバルト（ＣｏＷＯ4）を担持してなる、水分解反応用の触媒が提供される。 In order to solve the above problems, according to the present invention, there is provided a catalyst for water splitting reaction, in which cobalt tungstate (CoWO 4 ) is supported on tungsten oxide (WO 3 ) as a support.
本発明によれば、担体としての酸化タングステン上にタングステン酸コバルトを担持してなる本発明の水分解反応用の触媒のように、タングステン酸コバルトを酸化タングステンと組み合わせて用いることにより、タングステン酸コバルトを単独で用いた場合と比較して、水分解性が向上する。 According to the present invention, cobalt tungstate is used in combination with tungsten oxide like the catalyst for water splitting reaction of the present invention in which cobalt tungstate is supported on tungsten oxide as a support. Compared with the case where is used alone, water decomposability is improved.
本発明の水分解反応用の触媒は、担体としての酸化タングステン上にタングステン酸コバルトを担持してなることを特徴とする。 The catalyst for water splitting reaction of the present invention is characterized in that cobalt tungstate is supported on tungsten oxide as a carrier.
本明細書において「触媒」とは、化学電気分解反応（又は他の電気化学反応）の速度を高め、電気分解の一部としてそれ自身反応を受けるが、その反応によりほとんど消費されず、多くの化学変化に関与する材料を意味する。本発明の触媒材料は数回の使用の間にわずかの量消費され、多くの態様においてその当初の化学状態に再生される。 As used herein, “catalyst” refers to increasing the rate of a chemical electrolysis reaction (or other electrochemical reaction) and undergoing the reaction itself as part of the electrolysis, but is hardly consumed by the reaction. It means a material involved in chemical changes. The catalyst material of the present invention is consumed in small quantities during several uses and is regenerated to its original chemical state in many embodiments.
本発明において、タングステン酸コバルト触媒は、複数の非晶質タングステン酸コバルトナノ粒子を含む。ある場合には、このナノ粒子はサイズが均一であり、１００ｎｍ未満の平均粒度を有する。 In the present invention, the cobalt tungstate catalyst includes a plurality of amorphous cobalt tungstate nanoparticles. In some cases, the nanoparticles are uniform in size and have an average particle size of less than 100 nm.
担体としての酸化タングステンは、特に制限はなく、粒径２００ｎｍ〜２μｍ程度の粒子を用いる。この酸化タングステン担体に、当該分野において公知の方法によりタングステン酸コバルト触媒を担持させることにより、本発明の水分解反応用触媒が得られる。 Tungsten oxide as a carrier is not particularly limited, and particles having a particle size of about 200 nm to 2 μm are used. By supporting the cobalt tungstate catalyst on the tungsten oxide support by a method known in the art, the water splitting reaction catalyst of the present invention can be obtained.
本発明の水分解反応用触媒におけるタングステン酸コバルト触媒の濃度は、好ましくは５〜４０ｗｔ％、特に好ましくは７〜３７ｗｔ％である。 The concentration of the cobalt tungstate catalyst in the catalyst for water splitting reaction of the present invention is preferably 5 to 40 wt%, particularly preferably 7 to 37 wt%.
本発明を以下の実施例によりさらに説明するが、この例は本発明の範囲を限定するものではない。 The invention is further illustrated by the following examples, which do not limit the scope of the invention.
実施例１
ＣｏＷＯ4／ＷＯ3の合成
担体としての酸化タングステン（ＷＯ3）を水に分散させ、この分散液に硝酸コバルト（Ｃｏ(ＮＯ3)2）水溶液を加え、続けてタングステン酸ナトリウム（Ｎａ2ＷＯ4）水溶液を、Ｃｏ：Ｗのモル比が１：１となるように加え、１〜２時間撹拌した。この溶液を真空濾過し、ろ紙上の粉末を水洗後、１２０℃にて一晩乾燥させた。乾燥させた粉末を粉砕後、２５０℃Ａｒ雰囲気下で１時間焼成し、ＣｏＷＯ4／ＷＯ3を得た。ＣｏＷＯ4が全重量を基準として７ｗｔ％、２６ｗｔ％及び４６ｗｔ％になるように担持させ、また担持されているＣｏ量はＩＣＰにより定量した。得られた７ｗｔ％担持量のＣｏＷＯ4／ＷＯ3のＴＥＭ（透過型電子顕微鏡）像を図１に示す。
Example 1
Synthesis of CoWO 4 / WO 3 Tungsten oxide (WO 3 ) as a carrier is dispersed in water, an aqueous solution of cobalt nitrate (Co (NO 3 ) 2 ) is added to this dispersion, and then sodium tungstate (Na 2 WO 4). ) The aqueous solution was added so that the molar ratio of Co: W was 1: 1 and stirred for 1-2 hours. This solution was vacuum filtered, and the powder on the filter paper was washed with water and dried at 120 ° C. overnight. The dried powder was pulverized and then fired in an Ar atmosphere at 250 ° C. for 1 hour to obtain CoWO 4 / WO 3 . CoWO 4 was supported at 7 wt%, 26 wt% and 46 wt% based on the total weight, and the amount of Co supported was quantified by ICP. FIG. 1 shows a TEM (transmission electron microscope) image of the obtained 7 wt% CoWO 4 / WO 3 .
なお、このＩＣＰとは、誘導結合プラズマ発行分光分析装置（ＩＣＰ−ＡＥＳ）を用いた方法であり、石英ガラス製の放電管（トーチ）に巻き付けた誘導コイルに高周波電流を流すことによって誘導磁場を発生させ、そこにアルゴンガスを導入してプラズマ状態とし、ネブライザなどで霧状にした溶液試料をアルゴンプラズマ中に導入すると、溶液中に存在していた金属元素、半金属元素は、６０００〜７０００℃の熱で原子化されるとともに励起され、その後、基底状態に戻るときに各元素固有の波長の光を放出するため、この発光線を検出することにより、波長から定性分析を、発光強度から定量分析を行うものである。 The ICP is a method using an inductively coupled plasma emission spectroscopic analyzer (ICP-AES). An induction magnetic field is generated by flowing a high-frequency current through an induction coil wound around a discharge tube (torch) made of quartz glass. When an argon gas is introduced into a plasma state and a solution sample atomized by a nebulizer or the like is introduced into the argon plasma, the metal elements and metalloid elements present in the solution are 6000 to 7000. Since it is atomized and excited by heat at ℃, and then emits light of each element's unique wavelength when returning to the ground state, by detecting this emission line, qualitative analysis from wavelength can be performed from emission intensity. Quantitative analysis is performed.
比較例１
ＣｏＷＯ4の合成
硝酸コバルト（Ｃｏ(ＮＯ3)2）水溶液にタングステン酸ナトリウム（Ｎａ2ＷＯ4）水溶液を、Ｃｏ：Ｗのモル比が１：１となるように加え、１〜２時間撹拌した。この溶液を真空濾過し、ろ紙上の粉末を水洗後、１２０℃にて一晩乾燥させた。乾燥させた粉末を粉砕後、２５０℃Ａｒ雰囲気下で１時間焼成することによりＣｏＷＯ4を得た。
Comparative Example 1
Synthesis of CoWO 4 An aqueous solution of sodium tungstate (Na 2 WO 4 ) was added to an aqueous solution of cobalt nitrate (Co (NO 3 ) 2 ) so that the molar ratio of Co: W was 1: 1 and stirred for 1 to 2 hours. . This solution was vacuum filtered, and the powder on the filter paper was washed with water and dried at 120 ° C. overnight. The dried powder was pulverized and then fired in an Ar atmosphere at 250 ° C. for 1 hour to obtain CoWO 4 .
比較例２及び３
ＣｏＷＯ4／Ｇａ2Ｏ3（比較例２）及びＣｏＷＯ4／ＴｉＯ2（比較例３）の合成
担体としての酸化ガリウム（Ｇａ2Ｏ3、比較例２）及びチタニア（ＴｉＯ2、比較例３）を水に分散させ、この分散液に硝酸コバルト（Ｃｏ(ＮＯ3)2）水溶液を加え、続けてタングステン酸ナトリウム（Ｎａ2ＷＯ4）水溶液を、Ｃｏ：Ｗのモル比が１：１となるように加え、１〜２時間撹拌した。この溶液を真空濾過し、ろ紙上の粉末を水洗後、１２０℃にて一晩乾燥させた。乾燥させた粉末を粉砕後、２５０℃Ａｒ雰囲気下で１時間焼成し、ＣｏＷＯ4／Ｇａ2Ｏ3（比較例２）及びＣｏＷＯ4／ＴｉＯ2を得た。ＣｏＷＯ4が全重量を基準として７ｗｔ％になるように担持させ、また担持されているＣｏ量はＩＣＰにより定量した。
Comparative Examples 2 and 3
Synthesis of CoWO 4 / Ga 2 O 3 (Comparative Example 2) and CoWO 4 / TiO 2 (Comparative Example 3) Gallium oxide (Ga 2 O 3 , Comparative Example 2) and titania (TiO 2 , Comparative Example 3) as carriers Is dispersed in water, an aqueous solution of cobalt nitrate (Co (NO 3 ) 2 ) is added to the dispersion, and then an aqueous solution of sodium tungstate (Na 2 WO 4 ) is added at a molar ratio of Co: W of 1: 1. And stirred for 1-2 hours. This solution was vacuum filtered, and the powder on the filter paper was washed with water and dried at 120 ° C. overnight. The dried powder was pulverized and then fired in an Ar atmosphere at 250 ° C. for 1 hour to obtain CoWO 4 / Ga 2 O 3 (Comparative Example 2) and CoWO 4 / TiO 2 . CoWO 4 was supported at 7 wt% based on the total weight, and the amount of Co supported was quantified by ICP.
触媒活性の評価
図２に水分解反応用触媒の酸素発生活性を定量化する反応系を示す。反応水溶液中の光増感錯体（ルテニウムトリス(2,2'-ビピリジル）過塩素酸塩）が光を吸収し、励起された電子を犠牲酸化剤（Ｎａ2Ｓ2Ｏ8）に渡して３価のルテニウム錯体になる。この３価のルテニウム錯体のホールへ、水分解によって生成した電子が再結合し、光増感錯体は２価のルテニウム錯体へ戻るとともに酸素が発生する。ここで、反応水溶液の条件を以下の表１に示す。なお、水溶液中で触媒が高分散の状態になるように、触媒に緩衝液を加えたものを２分間超音波洗浄機にかけ、さらにボルテックスミキサーによって撹拌、分散させて溶液を調製した。
Evaluation of Catalyst Activity FIG. 2 shows a reaction system for quantifying the oxygen generation activity of the water splitting reaction catalyst. The photosensitizing complex (ruthenium tris (2,2'-bipyridyl) perchlorate) in the reaction aqueous solution absorbs light and passes the excited electrons to the sacrificial oxidant (Na 2 S 2 O 8 ). It becomes a valent ruthenium complex. Electrons generated by water splitting recombine with the holes of the trivalent ruthenium complex, and the photosensitized complex returns to the divalent ruthenium complex and oxygen is generated. Here, the conditions of the reaction aqueous solution are shown in Table 1 below. A solution prepared by adding a buffer solution to the catalyst in an ultrasonic cleaner for 2 minutes and further stirring and dispersing with a vortex mixer so that the catalyst was highly dispersed in the aqueous solution.
発生する酸素（溶存酸素）は、図３に示すクラーク型酸素電極計測システム１にて計測した。２５℃の温水を循環させたチャンバー２内に反応水溶液３を２ｍｌ入れ、撹拌子４にて撹拌しながら１００Ｗキセノンランプにて光照射した。溶液がある位置での光照射強度は、あらかじめ太陽光スペクトロメーターで計測しておき、５５０Ｗ／ｍ2であった。溶液中の溶存酸素が酸素透過膜５を透過し、飽和ＫＣｌ溶液６中に拡散すると、０．６Ｖの電圧を印加したＡｇ電極７及びＰｔ電極８上において以下の反応が起き、起電力が生ずる。 Oxygen to be generated (dissolved oxygen) was measured by a Clark type oxygen electrode measurement system 1 shown in FIG. 2 ml of the aqueous reaction solution 3 was placed in the chamber 2 in which warm water of 25 ° C. was circulated, and irradiated with light with a 100 W xenon lamp while stirring with the stirrer 4. The light irradiation intensity at a position where the solution was present was measured in advance with a sunlight spectrometer and was 550 W / m 2 . When dissolved oxygen in the solution permeates the oxygen permeable membrane 5 and diffuses into the saturated KCl solution 6, the following reaction occurs on the Ag electrode 7 and the Pt electrode 8 to which a voltage of 0.6 V is applied, and an electromotive force is generated. .
Ｐｔ電極：Ｏ2＋４Ｈ+＋４ｅ- → ２Ｈ2Ｏ
Ａｇ電極：４Ａｇ＋４Ｃｌ- → ４ＡｇＣｌ＋４ｅ-
Pt electrode: O 2 + 4H + + 4e − → 2H 2 O
Ag electrode: 4Ag + 4Cl − → 4AgCl + 4e −
この起電力を換算して、溶存酸素濃度を求める。この溶存酸素濃度への換算には、以下の表２に示す２５℃での溶存酸素濃度での起電力量と、ジチオナイト（チオ硫酸ナトリム）で溶存酸素を還元し、溶存酸素量をゼロにしたときの起電力量の差を用いる。酸素発生速度は、得られた酸素発生量の時間変化の曲線の傾きが最大になるところより求めた（図４）。 The electromotive force is converted to obtain the dissolved oxygen concentration. In conversion to this dissolved oxygen concentration, the amount of electromotive force at the dissolved oxygen concentration at 25 ° C. shown in Table 2 below and the dissolved oxygen was reduced with dithionite (sodium thiosulfate) to reduce the dissolved oxygen amount to zero. The difference in the amount of electromotive force is used. The oxygen generation rate was obtained from the point at which the slope of the curve of the obtained oxygen generation amount with time was maximized (FIG. 4).
図５に実施例及び比較例における酸素発生速度の触媒濃度依存性を、図６に実施例１の酸素発生速度の触媒担持量依存性を示す。図５に示すように、いずれの触媒も、触媒濃度の増加とともに酸素発生速度が大きくなっていることから、図２に示す活性評価系において、水分解反応が酸素発生速度を決定していると考えられ、触媒の能力を比較することができると考えられる。図５の結果より、すべての濃度領域において、酸化タングステン担体にタングステン酸コバルトを担持させたＣｏＷＯ4／ＷＯ3は、ＣｏＷＯ4単独よりも酸素発生速度が大きく、触媒活性が高くなっているといえる。一方、酸化タングステンと同様の光触媒である酸化ガリウム（Ｇａ2Ｏ3）及びチタニア（ＴｉＯ2）を担体として用いた触媒は、ＣｏＷＯ4単独よりも活性が低かった。また図６に示すように、同じＣｏ濃度であっても、２６ｗｔ％担持品が最も活性が高かった。 FIG. 5 shows the catalyst concentration dependency of the oxygen generation rate in Examples and Comparative Examples, and FIG. 6 shows the catalyst loading amount dependency of the oxygen generation rate in Example 1. As shown in FIG. 5, since the oxygen generation rate of each catalyst increases as the catalyst concentration increases, the water splitting reaction determines the oxygen generation rate in the activity evaluation system shown in FIG. It is thought that the ability of the catalyst can be compared. From the results shown in FIG. 5, it can be said that CoWO 4 / WO 3 in which cobalt tungstate is supported on a tungsten oxide carrier has a higher oxygen generation rate and higher catalytic activity than CoWO 4 alone in all concentration regions. . On the other hand, a catalyst using gallium oxide (Ga 2 O 3 ) and titania (TiO 2 ), which are photocatalysts similar to tungsten oxide, was less active than CoWO 4 alone. Moreover, as shown in FIG. 6, even if it was the same Co density | concentration, the 26 wt% support | carrier goods had the highest activity.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013261473A JP2015116535A (en) | 2013-12-18 | 2013-12-18 | Catalyst for water-splitting reaction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013261473A JP2015116535A (en) | 2013-12-18 | 2013-12-18 | Catalyst for water-splitting reaction |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2015116535A true JP2015116535A (en) | 2015-06-25 |
Family
ID=53529790
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2013261473A Pending JP2015116535A (en) | 2013-12-18 | 2013-12-18 | Catalyst for water-splitting reaction |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2015116535A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106179392A (en) * | 2016-07-19 | 2016-12-07 | 温州大学 | A kind of preparation method of the cobaltous tungstate nanometer rods eelctro-catalyst of iron ion doping |
| CN109806902A (en) * | 2019-02-28 | 2019-05-28 | 陕西科技大学 | A kind of W18O49/NiWO4The preparation method of/NF self-supporting electrocatalysis material |
| CN113713826A (en) * | 2021-09-15 | 2021-11-30 | 辽宁大学 | Fe3+/CoWO4Composite acoustic catalyst and preparation method and application thereof |
| CN113713830A (en) * | 2021-09-15 | 2021-11-30 | 辽宁大学 | CoWO for degrading dye4/Ag2O composite acoustic catalyst and preparation method and application thereof |
| JP2021186750A (en) * | 2020-05-29 | 2021-12-13 | 国立大学法人山口大学 | Catalyst for oxygen evolution reaction and method for producing the same |
| CN114653383A (en) * | 2022-04-01 | 2022-06-24 | 浙江大学 | Indium zinc sulfide photocatalyst with surface modified by cobalt tungstate and cobaltosic oxide together and preparation method and application thereof |
| CN114808013A (en) * | 2022-05-06 | 2022-07-29 | 台州学院 | Tungsten trioxide/manganese tungstate/cobalt tungstate photoelectrode material and preparation method and application thereof |
| CN115700300A (en) * | 2022-11-25 | 2023-02-07 | 安徽工业大学 | Multi-element transition metal compound electrocatalyst material and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005068007A (en) * | 2004-10-18 | 2005-03-17 | National Institute Of Advanced Industrial & Technology | Method for manufacturing hydrogen and oxygen by iodine compound and semiconductor photocatalyst |
| JP2005170780A (en) * | 2003-11-18 | 2005-06-30 | Japan Science & Technology Agency | Apparatus and method of decomposing water and mechanocatalyst for water decomposition |
| JP2011173102A (en) * | 2010-02-25 | 2011-09-08 | Mitsubishi Chemicals Corp | Photocatalyst for water photolysis reaction and method for producing the same |
| JP2013155106A (en) * | 2012-01-31 | 2013-08-15 | Toyota Motor Engineering & Manufacturing North America Inc | Water oxidation catalyst |
| JP2013154333A (en) * | 2012-01-31 | 2013-08-15 | Toyota Motor Corp | Method and apparatus for producing hydrogen and oxygen by decomposing water with photocatalyst |
-
2013
- 2013-12-18 JP JP2013261473A patent/JP2015116535A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005170780A (en) * | 2003-11-18 | 2005-06-30 | Japan Science & Technology Agency | Apparatus and method of decomposing water and mechanocatalyst for water decomposition |
| JP2005068007A (en) * | 2004-10-18 | 2005-03-17 | National Institute Of Advanced Industrial & Technology | Method for manufacturing hydrogen and oxygen by iodine compound and semiconductor photocatalyst |
| JP2011173102A (en) * | 2010-02-25 | 2011-09-08 | Mitsubishi Chemicals Corp | Photocatalyst for water photolysis reaction and method for producing the same |
| JP2013155106A (en) * | 2012-01-31 | 2013-08-15 | Toyota Motor Engineering & Manufacturing North America Inc | Water oxidation catalyst |
| JP2013154333A (en) * | 2012-01-31 | 2013-08-15 | Toyota Motor Corp | Method and apparatus for producing hydrogen and oxygen by decomposing water with photocatalyst |
Non-Patent Citations (3)
| Title |
|---|
| FENG, Y. ET AL: "Sol-Flame Synthesis: A General Strategy To Decorate Nanowires with Metal Oxide/Noble Metal Nanoparti", NANO LETT., vol. 13, no. 3, JPN6016042882, 11 April 2012 (2012-04-11), pages 855 - 860, ISSN: 0003435179 * |
| FENG, Y. ET AL: "Sol-Flame Synthesis: A General Strategy To Decorate Nanowires with Metal Oxide/Noble Metal Nanoparti", NANO LETT., vol. 13, no. 3, JPN6016042884, 11 April 2012 (2012-04-11), pages 855 - 860, ISSN: 0003435180 * |
| SHAO, G. ET AL: "The preparation of CoWO4/WO3 nanocomposite powder", JOURNAL OF WUHAN UNIVERSITY OF TECHNOLOGY-MATER. SCI. ED., vol. 19, no. 2, JPN6016042886, June 2004 (2004-06-01), pages 1 - 3, ISSN: 0003435181 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106179392A (en) * | 2016-07-19 | 2016-12-07 | 温州大学 | A kind of preparation method of the cobaltous tungstate nanometer rods eelctro-catalyst of iron ion doping |
| CN109806902A (en) * | 2019-02-28 | 2019-05-28 | 陕西科技大学 | A kind of W18O49/NiWO4The preparation method of/NF self-supporting electrocatalysis material |
| CN109806902B (en) * | 2019-02-28 | 2021-07-06 | 陕西科技大学 | W18O49/NiWO4Preparation method of/NF self-supporting electrocatalytic material |
| JP2021186750A (en) * | 2020-05-29 | 2021-12-13 | 国立大学法人山口大学 | Catalyst for oxygen evolution reaction and method for producing the same |
| JP7444445B2 (en) | 2020-05-29 | 2024-03-06 | 国立大学法人山口大学 | Catalyst for oxygen evolution reaction and method for producing the same |
| CN113713826A (en) * | 2021-09-15 | 2021-11-30 | 辽宁大学 | Fe3+/CoWO4Composite acoustic catalyst and preparation method and application thereof |
| CN113713830A (en) * | 2021-09-15 | 2021-11-30 | 辽宁大学 | CoWO for degrading dye4/Ag2O composite acoustic catalyst and preparation method and application thereof |
| CN114653383A (en) * | 2022-04-01 | 2022-06-24 | 浙江大学 | Indium zinc sulfide photocatalyst with surface modified by cobalt tungstate and cobaltosic oxide together and preparation method and application thereof |
| CN114808013A (en) * | 2022-05-06 | 2022-07-29 | 台州学院 | Tungsten trioxide/manganese tungstate/cobalt tungstate photoelectrode material and preparation method and application thereof |
| CN115700300A (en) * | 2022-11-25 | 2023-02-07 | 安徽工业大学 | Multi-element transition metal compound electrocatalyst material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2015116535A (en) | Catalyst for water-splitting reaction | |
| Fan et al. | High-efficiency photoelectrocatalytic hydrogen generation enabled by Ag deposited and Ce doped TiO2 nanotube arrays | |
| Chen et al. | The role of CuO in promoting photocatalytic hydrogen production over TiO2 | |
| Momeni et al. | Cobalt modified tungsten–titania nanotube composite photoanodes for photoelectrochemical solar water splitting | |
| Ge et al. | In situ synthesis of cobalt–phosphate (Co–Pi) modified g-C3N4 photocatalysts with enhanced photocatalytic activities | |
| Antony et al. | Efficient photocatalytic hydrogen generation by Pt modified TiO2 nanotubes fabricated by rapid breakdown anodization | |
| Xie et al. | Long‐lived, visible‐light‐excited charge carriers of TiO2/BiVO4 nanocomposites and their unexpected photoactivity for water splitting | |
| Liu et al. | A critical study of the generality of the two step two electron pathway for water splitting by application of a C 3 N 4/MnO 2 photocatalyst | |
| Hou et al. | Efficient visible-light-driven photocatalytic hydrogen production using CdS@ TaON core–shell composites coupled with graphene oxide nanosheets | |
| CN110947376B (en) | Monoatomic noble metal anchoring defect type WO3/TiO2Nanotubes, their preparation and use | |
| Si et al. | Sub-nanometer Co 3 O 4 clusters anchored on TiO 2 (B) nano-sheets: Pt replaceable Co-catalysts for H 2 evolution | |
| Bi et al. | Construction of g-C3N4/TiO2 nanotube arrays Z-scheme heterojunction to improve visible light catalytic activity | |
| Xu et al. | Improving photo-oxidation activity of water by introducing Ti3+ in self-ordered TiO2 nanotube arrays treated with Ar/NH3 | |
| Ke et al. | ZrO2/g-C3N4 with enhanced photocatalytic degradation of methylene blue under visible light irradiation | |
| JP4997454B2 (en) | Semiconductor electrode and energy conversion system using the same | |
| Rawal et al. | Novel ZnFe2O4/WO3, a highly efficient visible-light photocatalytic system operated by a Z-scheme mechanism | |
| He et al. | Highly efficient and stable Ag/AgIO 3 particles for photocatalytic reduction of CO 2 under visible light | |
| US8968534B2 (en) | Water oxidation catalyst | |
| Vosoughi et al. | Novel ternary g-C3N4 nanosheet/Ag2MoO4/AgI photocatalysts: impressive photocatalysts for removal of various contaminants | |
| KR102449541B1 (en) | Photocatalyst comprising bimetallic nanoparticle and graphene oxide for denitrification reaction, and water treatment method using same | |
| Fiorenza et al. | Solar photocatalytic H2 production over CeO2-based catalysts: Influence of chemical and structural modifications | |
| Ibrahim et al. | Enhanced hydrogen evolution reaction on highly stable titania‐supported PdO and Eu2O3 nanocomposites in a strong alkaline solution | |
| Mandari et al. | Solar light response with noble metal-free highly active copper (II) phosphate/titanium dioxide nanoparticle/copper (II) oxide nanocomposites for photocatalytic hydrogen production | |
| Feng et al. | Architecting epitaxial-lattice-mismatch-free (LMF) zinc oxide/bismuth oxyiodide nano-heterostructures for efficient photocatalysis | |
| Pan et al. | Plasmon-engineered anti-replacement synthesis of naked Cu nanoclusters with ultrahigh electrocatalytic activity |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20160201 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20161026 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20161108 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20170509 |