JP2016536129A - 効率的水素放出のために拘束された遷移金属が促進する光触媒系 - Google Patents
効率的水素放出のために拘束された遷移金属が促進する光触媒系 Download PDFInfo
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- JP2016536129A JP2016536129A JP2016539668A JP2016539668A JP2016536129A JP 2016536129 A JP2016536129 A JP 2016536129A JP 2016539668 A JP2016539668 A JP 2016539668A JP 2016539668 A JP2016539668 A JP 2016539668A JP 2016536129 A JP2016536129 A JP 2016536129A
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 29
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 18
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- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
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- 229910052703 rhodium Inorganic materials 0.000 description 1
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- ZGHLCBJZQLNUAZ-UHFFFAOYSA-N sodium sulfide nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[Na+].[S-2] ZGHLCBJZQLNUAZ-UHFFFAOYSA-N 0.000 description 1
- XMUHNMQFDVIWGU-UHFFFAOYSA-M sodium;2,3-bis(sulfanyl)propane-1-sulfonate;hydrate Chemical compound O.[Na+].[O-]S(=O)(=O)CC(S)CS XMUHNMQFDVIWGU-UHFFFAOYSA-M 0.000 description 1
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Classifications
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/226—Sulfur, e.g. thiocarbamates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2265—Carbenes or carbynes, i.e.(image)
- B01J31/2269—Heterocyclic carbenes
- B01J31/2273—Heterocyclic carbenes with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
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- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/065—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents from a hydride
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
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- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Catalysts (AREA)
Abstract
Description
かなり多数の異なった半導体光触媒材料は、意図された用途に適している限り、本発明において使用可能である。例えば、半導体光触媒材料は、限定されるものではないが、CdS、MoS2、FeS、CoS、NiS、MnS2、ZnS、ZnS2、Cu2S、Rh2S、Ag2S、HgS、In2S3、SnS2、PbS、SnS2、PbS、SnS、TiS、Sb2S3などの一つ以上の硫化物を含む。典型的な一実施例において、半導体光触媒材料は、硫化カドミウム(CdS)の形態である。知られているように、硫化カドミウムは、半導体光触媒として機能する直接バンドギャップ半導体であり、太陽光セルやその他の用途の根本要素としてしばしば用いられる。CdS材料は、限定されるものではないが、高結晶性のCdS(CdSナノ結晶)を製造する合成技術などの従来技術を用いて調製される。
この方法には、ニッケル(後期遷移金属)などの金属(例えば、遷移金属)を半導体光触媒材料の表面に付着させるための分子リンカーの使用が含まれる。本発明の意図される用途に適したその他の遷移金属と関連材料としては、限定されるものではないが、Ag、Au、Pb、Ru、Ir、Cu、Fe、Mn、Co、Pt/Au合金が挙げられる。本出願人は、1,2−エタンジチオール(EDT)が遷移金属錯体を硫化カドミウム表面(半導体材料の表面)に付着させるための優れた分子リンカー(有機配位子)として機能することを見出した。1,2−エタンジチオール(EDT)は、式がC2H4(SH)2の無色の液体であって、金属イオンの優れた配位子として作用する。本発明の意図される用途に適したその他の有機配位子(分子リンカー)としては、限定されるものではないが、2−メルカプトプロピオン酸、チオグリコール酸、11−メルカプトウンデカン酸、メルカプトコハク酸、1,4−ベンゼンジチオール、4,4’−ジメルカプトスチルベン、p−フェニレンジアミン、4−メルカプト安息香酸、2,3−ジメルカプトプロパンスルホン酸ナトリウム一水和物、1,3,4−チアジアゾール−2,5−ジチオール、トリチオシアヌル酸、ビフェニル−4,4−ジチオール、(3−メルカプトプロピル)トリエトキシシランが挙げられる。
Claims (25)
- 最初の半導体光触媒材料を形成するステップと、
前記最初の光触媒材料を、有機配位子を含む第1の溶液に曝し、前記有機配位子が表面に堆積した光触媒材料を形成するステップと、
前記有機配位子が堆積した前記光触媒材料を、金属水溶液に懸濁させ、金属−有機配位子種が堆積した光触媒材料を形成するステップと
を備えた光触媒の製造方法。 - 前記最初の光触媒材料がCdSからなる請求項1記載の方法。
- 前記最初のCdS光触媒材料が合成CdSナノ結晶からなる請求項2記載の方法。
- 前記有機配位子が1,2−エタンジチオール(EDT)である請求項1記載の方法。
- 前記金属水溶液が遷移金属からなる請求項1記載の方法。
- 前記遷移金属がNi2+からなる請求項5記載の方法。
- 前記有機配位子で前記光触媒材料の表面を確実に飽和させるために十分な時間、前記最初の光触媒材料が前記有機配位子を含む溶液に曝される請求項1記載の方法。
- 前記十分な時間が少なくとも約6時間である請求項7記載の方法。
- 前記第1の溶液が1,2−エタンジチオール(EDT)のエタノール溶液である請求項1記載の方法。
- 表面に前記有機配位子を有する前記光触媒材料が前記金属水溶液に懸濁される前に濾過される請求項1記載の方法。
- 前記光触媒材料を懸濁させるステップがさらに所定の時間、前記金属水溶液を撹拌するステップを備えた請求項1記載の方法。
- 前記所定の時間が少なくとも6時間である請求項11記載の方法。
- 前記光触媒が(1)H2Sからの水素放出、(2)水分解、(3)CO2還元ができる請求項1記載の方法。
- 光触媒材料を準備するステップと、
ドーパント層を形成することなく遷移金属種を前記光触媒材料の表面に取り付けるために有機配位子を用いるステップと
を備えたH2Sを水素と硫黄に変換することが可能な光触媒の製造方法。 - 前記光触媒材料がCdSである請求項14記載の方法。
- 前記有機配位子が1,2−エタンジチオール(EDT)からなる請求項14記載の方法。
- 前記遷移金属がNi2+からなる請求項14記載の方法。
- 前記遷移金属種が後期遷移金属種からなる請求項14記載の方法。
- 前記遷移金属種を取り付けるために前記有機配位子を用いる前記ステップは、
CdS光触媒材料を含む第1の溶液に1,2−エタンジチオール(EDT)を加えて第1の混合物を得るステップと、
前記第1の混合物からCdSの沈殿を得るステップと、
前記CdSを第2の溶液に再び分散させて懸濁液を得るステップと、
前記懸濁液にNi(NO3)2を加えるステップと、
Ni−EDT種が表面に取り付けられたCdS光触媒材料を得るステップと
を備えた請求項15記載の方法。 - 前記第1及び第2の溶液がメタノールからなる請求項19記載の方法。
- 請求項14記載の方法に従って製造された光触媒。
- H2Sを水素と硫黄に変換することが可能であって、以下の式を有する光触媒。
- H2Sから水素を発生させるために基質表面にNi−1,2−エタンジチオール(EDT)複合体を堆積させた光触媒を用いるステップを備えたH2Sから水素を放出するための方法。
- 前記基質が半導体基質からなる請求項23記載の方法。
- 前記半導体基質がCdS材料からなる請求項24記載の方法。
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10226779A (ja) * | 1996-12-12 | 1998-08-25 | Mitsui Chem Inc | 半導体超微粒子反応試剤 |
JP2001239164A (ja) * | 2000-02-29 | 2001-09-04 | Korea Res Inst Of Chemical Technology | 硫化カドミウム系水素発生用光触媒及びその製造方法とそれを用いる水素の製造方法 |
JP2003502148A (ja) * | 1999-06-18 | 2003-01-21 | チョング カンパニーリミテッド | 水素発生用硫化カドミウム系光触媒の製造方法とそれによる水素の製造方法 |
JP2003265962A (ja) * | 2002-03-18 | 2003-09-24 | Nittetsu Mining Co Ltd | 光触媒およびその製造方法 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3782978A (en) * | 1971-07-06 | 1974-01-01 | Shipley Co | Electroless nickel plating |
CN101293632A (zh) | 2007-04-25 | 2008-10-29 | 中国科学院大连化学物理研究所 | 一种光催化分解h2s转化为氢气和硫的方法 |
CN103073049A (zh) * | 2011-10-26 | 2013-05-01 | 上海纳米技术及应用国家工程研究中心有限公司 | 一种硫化镉多级结构纳米材料的络合剂辅助制备方法 |
CN102861597B (zh) * | 2012-09-27 | 2014-08-13 | 中国海洋石油总公司 | 一种响应可见光的光解水制氢催化剂及其制备方法 |
CN103205300B (zh) * | 2013-04-17 | 2014-08-20 | 苏州方昇光电装备技术有限公司 | 一种抗磨损自修复的硫-金属纳米粒子的制备方法 |
-
2014
- 2014-09-04 US US14/477,414 patent/US9579639B2/en active Active
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10226779A (ja) * | 1996-12-12 | 1998-08-25 | Mitsui Chem Inc | 半導体超微粒子反応試剤 |
JP2003502148A (ja) * | 1999-06-18 | 2003-01-21 | チョング カンパニーリミテッド | 水素発生用硫化カドミウム系光触媒の製造方法とそれによる水素の製造方法 |
JP2001239164A (ja) * | 2000-02-29 | 2001-09-04 | Korea Res Inst Of Chemical Technology | 硫化カドミウム系水素発生用光触媒及びその製造方法とそれを用いる水素の製造方法 |
JP2003265962A (ja) * | 2002-03-18 | 2003-09-24 | Nittetsu Mining Co Ltd | 光触媒およびその製造方法 |
Non-Patent Citations (1)
Title |
---|
JIN-OOK BAEG: "A novel nanoscale semiconductor photocatalyst for solar hydrogen production", SPIE NEWSROOM, JPN5016009680, 1 January 2008 (2008-01-01), ISSN: 0003702734 * |
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