Homogeneous catalytic reduction of polyoxometalate by hydrogen gas with a hydrogenase model complex

研究成果: ジャーナルへの寄稿記事

抄録

The homogeneous catalytic reduction of a polyoxometalate (POM) by hydrogen gas in aqueous media was investigated for the first time by using a [NiRu] hydrogenase model complex (I) under very mild conditions. By bubbling hydrogen gas into the buffer solution containing I and the Dawson-type POM (IIox), the color of the solution turned from pale yellow to dark blue, suggesting the reduction of IIox. The catalytic and kinetic studies revealed that I acted as an efficient catalyst to yield one-electron-reduced Dawson-type POM (IIred) with a low energy barrier for activating dihydrogen and reducing IIoxvia a hydride complex of I. The process for the one-electron reduction of IIox was confirmed by UV-vis spectroscopy, controlled potential electrolysis, and X-ray photoelectron spectroscopy. POM IIred could stably store protons and electrons and release them by addition of oxidants, demonstrating that POMs acted as redox active mediators for transporting protons and electrons from hydrogen gas to acceptors. The recycle study showed that IIox and IIred could be reduced and oxidized by hydrogen and oxygen gases, respectively, at least five times with >99% yield of reduced species, showing a durable system for extracting protons and electrons from hydrogen gas.

元の言語英語
ページ(範囲)19518-19522
ページ数5
ジャーナルRSC Advances
9
発行部数34
DOI
出版物ステータス出版済み - 1 1 2019

Fingerprint

Hydrogenase
Hydrogen
Gases
Electrons
Protons
Energy barriers
Ultraviolet spectroscopy
Oxidants
Electrolysis
Hydrides
Buffers
X ray photoelectron spectroscopy
polyoxometalate I
Oxygen
Color
Catalysts
Kinetics

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Chemical Engineering(all)

これを引用

Homogeneous catalytic reduction of polyoxometalate by hydrogen gas with a hydrogenase model complex. / Minato, Takuo; Matsumoto, Takahiro; Ogo, Seiji.

:: RSC Advances, 巻 9, 番号 34, 01.01.2019, p. 19518-19522.

研究成果: ジャーナルへの寄稿記事

@article{c0107af3a33844188a7cc04510c85e4a,
title = "Homogeneous catalytic reduction of polyoxometalate by hydrogen gas with a hydrogenase model complex",
abstract = "The homogeneous catalytic reduction of a polyoxometalate (POM) by hydrogen gas in aqueous media was investigated for the first time by using a [NiRu] hydrogenase model complex (I) under very mild conditions. By bubbling hydrogen gas into the buffer solution containing I and the Dawson-type POM (IIox), the color of the solution turned from pale yellow to dark blue, suggesting the reduction of IIox. The catalytic and kinetic studies revealed that I acted as an efficient catalyst to yield one-electron-reduced Dawson-type POM (IIred) with a low energy barrier for activating dihydrogen and reducing IIoxvia a hydride complex of I. The process for the one-electron reduction of IIox was confirmed by UV-vis spectroscopy, controlled potential electrolysis, and X-ray photoelectron spectroscopy. POM IIred could stably store protons and electrons and release them by addition of oxidants, demonstrating that POMs acted as redox active mediators for transporting protons and electrons from hydrogen gas to acceptors. The recycle study showed that IIox and IIred could be reduced and oxidized by hydrogen and oxygen gases, respectively, at least five times with >99{\%} yield of reduced species, showing a durable system for extracting protons and electrons from hydrogen gas.",
author = "Takuo Minato and Takahiro Matsumoto and Seiji Ogo",
year = "2019",
month = "1",
day = "1",
doi = "10.1039/c9ra04396a",
language = "English",
volume = "9",
pages = "19518--19522",
journal = "RSC Advances",
issn = "2046-2069",
publisher = "Royal Society of Chemistry",
number = "34",

}

TY - JOUR

T1 - Homogeneous catalytic reduction of polyoxometalate by hydrogen gas with a hydrogenase model complex

AU - Minato, Takuo

AU - Matsumoto, Takahiro

AU - Ogo, Seiji

PY - 2019/1/1

Y1 - 2019/1/1

N2 - The homogeneous catalytic reduction of a polyoxometalate (POM) by hydrogen gas in aqueous media was investigated for the first time by using a [NiRu] hydrogenase model complex (I) under very mild conditions. By bubbling hydrogen gas into the buffer solution containing I and the Dawson-type POM (IIox), the color of the solution turned from pale yellow to dark blue, suggesting the reduction of IIox. The catalytic and kinetic studies revealed that I acted as an efficient catalyst to yield one-electron-reduced Dawson-type POM (IIred) with a low energy barrier for activating dihydrogen and reducing IIoxvia a hydride complex of I. The process for the one-electron reduction of IIox was confirmed by UV-vis spectroscopy, controlled potential electrolysis, and X-ray photoelectron spectroscopy. POM IIred could stably store protons and electrons and release them by addition of oxidants, demonstrating that POMs acted as redox active mediators for transporting protons and electrons from hydrogen gas to acceptors. The recycle study showed that IIox and IIred could be reduced and oxidized by hydrogen and oxygen gases, respectively, at least five times with >99% yield of reduced species, showing a durable system for extracting protons and electrons from hydrogen gas.

AB - The homogeneous catalytic reduction of a polyoxometalate (POM) by hydrogen gas in aqueous media was investigated for the first time by using a [NiRu] hydrogenase model complex (I) under very mild conditions. By bubbling hydrogen gas into the buffer solution containing I and the Dawson-type POM (IIox), the color of the solution turned from pale yellow to dark blue, suggesting the reduction of IIox. The catalytic and kinetic studies revealed that I acted as an efficient catalyst to yield one-electron-reduced Dawson-type POM (IIred) with a low energy barrier for activating dihydrogen and reducing IIoxvia a hydride complex of I. The process for the one-electron reduction of IIox was confirmed by UV-vis spectroscopy, controlled potential electrolysis, and X-ray photoelectron spectroscopy. POM IIred could stably store protons and electrons and release them by addition of oxidants, demonstrating that POMs acted as redox active mediators for transporting protons and electrons from hydrogen gas to acceptors. The recycle study showed that IIox and IIred could be reduced and oxidized by hydrogen and oxygen gases, respectively, at least five times with >99% yield of reduced species, showing a durable system for extracting protons and electrons from hydrogen gas.

UR - http://www.scopus.com/inward/record.url?scp=85068229999&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85068229999&partnerID=8YFLogxK

U2 - 10.1039/c9ra04396a

DO - 10.1039/c9ra04396a

M3 - Article

AN - SCOPUS:85068229999

VL - 9

SP - 19518

EP - 19522

JO - RSC Advances

JF - RSC Advances

SN - 2046-2069

IS - 34

ER -