Photocatalytic CO2Reduction Using a Robust Multifunctional Iridium Complex toward the Selective Formation of Formic Acid

Kenji Kamada; Jieun Jung; Taku Wakabayashi; Keita Sekizawa; Shunsuke Sato; Takeshi Morikawa; Shunichi Fukuzumi; Susumu Saito

doi:10.1021/jacs.0c03097

Photocatalytic CO₂Reduction Using a Robust Multifunctional Iridium Complex toward the Selective Formation of Formic Acid

Kenji Kamada, Jieun Jung, Taku Wakabayashi, Keita Sekizawa, Shunsuke Sato, Takeshi Morikawa, Shunichi Fukuzumi, Susumu Saito

Department of Chemistry & Nanoscience

Research output: Contribution to journal › Article › peer-review

111 Scopus citations

Abstract

A highly efficient tetradentate PNNP-type Ir photocatalyst, Mes-IrPCY2, was developed for the reduction of carbon dioxide. The photocatalyst furnished formic acid (HCO2H) with 87% selectivity together with carbon monoxide to achieve a turnover number of 2560, which is the highest among CO2 reduction photocatalysts without an additional photosensitizer. Mes-IrPCY2 exhibited outstanding photocatalytic CO2 reduction activity in the presence of the sacrificial electron source 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole (BIH) in CO2-saturated N,N-dimethylacetamide under irradiation with visible light. The quantum yield was determined to be 49% for the generation of HCO2H and CO. Electron paramagnetic resonance and UV-vis spectroscopy studies of Mes-IrPCY2 with a sacrificial electron donor revealed that the one-electron-reduced species is the key intermediate for the selective formation of HCO2H.

Original language	English
Pages (from-to)	10261-10266
Number of pages	6
Journal	Journal of the American Chemical Society
Volume	142
Issue number	23
DOIs	https://doi.org/10.1021/jacs.0c03097
State	Published - 10 Jun 2020

Bibliographical note

Funding Information:
We thank Dr. Kin-ichi Oyama (Nagoya University) for elemental analysis. This work was supported by a Grant-in-Aid for Early-Career Scientists (18K14241 to J.J.), a Grant-in-Aid for Scientific Research (B) (19H02713 to S.S.), and a Grant-in-Aid (16H02268 to S.F.) from the Japanese Society for the Promotion of Science (JSPS), by the Asahi Glass Foundation (Step-Up Grant to S.S.), by a Grant-in-Aid for Scientific Research on Innovative Areas (18H04247 to S.S.) from the Japanese Ministry of Education, Culture, Sports, Science and Technology (MEXT), and by the Ministry of the Environment of the Government of Japan.

Publisher Copyright:
Copyright © 2020 American Chemical Society.

Access to Document

10.1021/jacs.0c03097

Cite this

@article{d77df2874f704feda1fd1f3ab1811df8,

title = "Photocatalytic CO2Reduction Using a Robust Multifunctional Iridium Complex toward the Selective Formation of Formic Acid",

abstract = "A highly efficient tetradentate PNNP-type Ir photocatalyst, Mes-IrPCY2, was developed for the reduction of carbon dioxide. The photocatalyst furnished formic acid (HCO2H) with 87% selectivity together with carbon monoxide to achieve a turnover number of 2560, which is the highest among CO2 reduction photocatalysts without an additional photosensitizer. Mes-IrPCY2 exhibited outstanding photocatalytic CO2 reduction activity in the presence of the sacrificial electron source 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole (BIH) in CO2-saturated N,N-dimethylacetamide under irradiation with visible light. The quantum yield was determined to be 49% for the generation of HCO2H and CO. Electron paramagnetic resonance and UV-vis spectroscopy studies of Mes-IrPCY2 with a sacrificial electron donor revealed that the one-electron-reduced species is the key intermediate for the selective formation of HCO2H.",

author = "Kenji Kamada and Jieun Jung and Taku Wakabayashi and Keita Sekizawa and Shunsuke Sato and Takeshi Morikawa and Shunichi Fukuzumi and Susumu Saito",

note = "Funding Information: We thank Dr. Kin-ichi Oyama (Nagoya University) for elemental analysis. This work was supported by a Grant-in-Aid for Early-Career Scientists (18K14241 to J.J.), a Grant-in-Aid for Scientific Research (B) (19H02713 to S.S.), and a Grant-in-Aid (16H02268 to S.F.) from the Japanese Society for the Promotion of Science (JSPS), by the Asahi Glass Foundation (Step-Up Grant to S.S.), by a Grant-in-Aid for Scientific Research on Innovative Areas (18H04247 to S.S.) from the Japanese Ministry of Education, Culture, Sports, Science and Technology (MEXT), and by the Ministry of the Environment of the Government of Japan. Publisher Copyright: Copyright {\textcopyright} 2020 American Chemical Society.",

year = "2020",

month = jun,

day = "10",

doi = "10.1021/jacs.0c03097",

language = "English",

volume = "142",

pages = "10261--10266",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "23",

}

TY - JOUR

T1 - Photocatalytic CO2Reduction Using a Robust Multifunctional Iridium Complex toward the Selective Formation of Formic Acid

AU - Kamada, Kenji

AU - Jung, Jieun

AU - Wakabayashi, Taku

AU - Sekizawa, Keita

AU - Sato, Shunsuke

AU - Morikawa, Takeshi

AU - Fukuzumi, Shunichi

AU - Saito, Susumu

N1 - Funding Information: We thank Dr. Kin-ichi Oyama (Nagoya University) for elemental analysis. This work was supported by a Grant-in-Aid for Early-Career Scientists (18K14241 to J.J.), a Grant-in-Aid for Scientific Research (B) (19H02713 to S.S.), and a Grant-in-Aid (16H02268 to S.F.) from the Japanese Society for the Promotion of Science (JSPS), by the Asahi Glass Foundation (Step-Up Grant to S.S.), by a Grant-in-Aid for Scientific Research on Innovative Areas (18H04247 to S.S.) from the Japanese Ministry of Education, Culture, Sports, Science and Technology (MEXT), and by the Ministry of the Environment of the Government of Japan. Publisher Copyright: Copyright © 2020 American Chemical Society.

PY - 2020/6/10

Y1 - 2020/6/10

N2 - A highly efficient tetradentate PNNP-type Ir photocatalyst, Mes-IrPCY2, was developed for the reduction of carbon dioxide. The photocatalyst furnished formic acid (HCO2H) with 87% selectivity together with carbon monoxide to achieve a turnover number of 2560, which is the highest among CO2 reduction photocatalysts without an additional photosensitizer. Mes-IrPCY2 exhibited outstanding photocatalytic CO2 reduction activity in the presence of the sacrificial electron source 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole (BIH) in CO2-saturated N,N-dimethylacetamide under irradiation with visible light. The quantum yield was determined to be 49% for the generation of HCO2H and CO. Electron paramagnetic resonance and UV-vis spectroscopy studies of Mes-IrPCY2 with a sacrificial electron donor revealed that the one-electron-reduced species is the key intermediate for the selective formation of HCO2H.

AB - A highly efficient tetradentate PNNP-type Ir photocatalyst, Mes-IrPCY2, was developed for the reduction of carbon dioxide. The photocatalyst furnished formic acid (HCO2H) with 87% selectivity together with carbon monoxide to achieve a turnover number of 2560, which is the highest among CO2 reduction photocatalysts without an additional photosensitizer. Mes-IrPCY2 exhibited outstanding photocatalytic CO2 reduction activity in the presence of the sacrificial electron source 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole (BIH) in CO2-saturated N,N-dimethylacetamide under irradiation with visible light. The quantum yield was determined to be 49% for the generation of HCO2H and CO. Electron paramagnetic resonance and UV-vis spectroscopy studies of Mes-IrPCY2 with a sacrificial electron donor revealed that the one-electron-reduced species is the key intermediate for the selective formation of HCO2H.

UR - http://www.scopus.com/inward/record.url?scp=85086356446&partnerID=8YFLogxK

U2 - 10.1021/jacs.0c03097

DO - 10.1021/jacs.0c03097

M3 - Article

C2 - 32456417

AN - SCOPUS:85086356446

SN - 0002-7863

VL - 142

SP - 10261

EP - 10266

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 23