バイオインスピレーションによるH2の生産用電気触媒におけるプロトンシャトルとしてのヘミラビルブリッジングチオラート
Shengda Ding1, Pokhraj Ghosh1, Allen M Lunsford1
1Department of Chemistry, Texas A & M University , College Station, Texas 77843, United States.
Journal of the American Chemical Society
|August 20, 2016
まとめ
研究者らは,水素生成のための電触媒で,陽子-電子と陽子-水素結合を調査した. Ni-FeとFe-Fe複合体は,金属と硫黄の結合分裂と効率的な結合のための特定の方向性を含むメカニズムで活性を示します.
科学分野:
- 無機化学
- 電気触媒
- バイオ有機化学
背景:
- 水素酵素は生物学的水素代謝に不可欠です.
- 合成のアナログは,電触媒の活性部位を模倣することを目的としています.
- 陽子-電子と陽子-水素結合を理解することは,効率的なH2生成の鍵です.
研究 の 目的:
- 合成電触媒における陽子-電子および陽子-水素結合を制御する特徴を調査する.
- [NiFe]ヒドロゲネーゼに触発された二金属複合体の構造-機能関係を探求する.
- H2生成のための活性電気触媒を特定し,その反応機構を明らかにする.
主な方法:
- 鉄成分と結合した二金属ディチオラト複合体 (MN2S2) の合成
- H2生成のための触媒活性を決定する電気化学分析.
- 電気化学的ポテンシャルと機械的パラメータを相関させるための計算研究.
主要な成果:
- Ni-Fe'とFe-Fe'バイメタリック複合体は,H2生成のための活性電気触媒として識別された.
- メカニズムは,電子吸収とFe-S結合の割れ分 (ヘミラビリティ) のための酸化還元活性NOリガンドを含む.
- 効率的な結合には,H2形成のための特定のヒドリドと陽子の方向性が必要であり,それは酸化還元レベルに依存する.
結論:
- 無害なNOリガンドは電子貯蔵に作用するが,水素形成には作用しない.
- Fe'-S結合分裂とチオラート溶解性は,陽子のシャトルとH2生成に不可欠である.
- 触媒の安定性は,金属の組成と望ましくない結合分裂の可能性 (例えば,Fe''-S) によって影響を受けます.
関連する概念動画
Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
4.0K
Catalytic hydrogenation of alkenes is a transition-metal catalyzed reduction of the double bond using molecular hydrogen to give alkanes. The mode of hydrogen addition follows syn stereochemistry.
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
4.0K
Preparation and Reactions of Thiols
7.8K
Thiols are prepared using the hydrosulfide anion as a nucleophile in a nucleophilic substitution reaction with alkyl halides. For instance, bromobutane reacts with sodium hydrosulfide to give butanethiol.
7.8K
Reduction of Alkenes: Catalytic Hydrogenation
14.7K
Alkenes undergo reduction by the addition of molecular hydrogen to give alkanes. Because the process generally occurs in the presence of a transition-metal catalyst, the reaction is called catalytic hydrogenation.
Metals like palladium, platinum, and nickel are commonly used in their solid forms — fine powder on an inert surface. As these catalysts remain insoluble in the reaction mixture, they are referred to as heterogeneous catalysts.
The hydrogenation process takes place on the...
Metals like palladium, platinum, and nickel are commonly used in their solid forms — fine powder on an inert surface. As these catalysts remain insoluble in the reaction mixture, they are referred to as heterogeneous catalysts.
The hydrogenation process takes place on the...
14.7K
Chemiosmosis
116.3K
Oxidative phosphorylation is a highly efficient process that generates large amounts of adenosine triphosphate (ATP), the basic unit of energy that drives many cellular processes. Oxidative phosphorylation involves two processes— the electron transport chain and chemiosmosis.
Electron Transport Chain
The electron transport chain involves a series of protein complexes on the inner mitochondrial membrane that undergo a series of redox reactions. At the end of this chain, the electrons...
Electron Transport Chain
The electron transport chain involves a series of protein complexes on the inner mitochondrial membrane that undergo a series of redox reactions. At the end of this chain, the electrons...
116.3K
Heterogeneous Catalysis
72
Heterogeneous catalysis involves a catalyst in a different phase from the reactants. It is a process where the catalyst and the reactants are in distinct phases, typically solid and gas or liquid.Most heterogeneous catalysts are metals, metal oxides, or acids. The list includes transition metals like iron (Fe), cobalt (Co), nickel (Ni), palladium (Pd), platinum (Pt), chromium (Cr), manganese (Mn), tungsten (W), silver (Ag), and copper (Cu). These metals possess partially vacant d orbitals that...
72
Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
9.3K
Introduction
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
9.3K


