TY - JOUR
T1 - Visible-light photocatalytic conversion of carbon dioxide by Ni(II) complexes with N4S2 coordination
T2 - Highly efficient and selective production of formate
AU - Lee, Sung Eun
AU - Nasirian, Azam
AU - Kim, Ye Eun
AU - Fard, Pegah Tavakoli
AU - Kim, Youngmee
AU - Jeong, Byeongmoon
AU - Kim, Sung Jin
AU - Baeg, Jin Ook
AU - Kim, Jinheung
N1 - Funding Information:
This work is supported by "Next Generation Carbon Upcycling Project" (Project 2017M1A2A2046740) through the National Research Foundation (NRF) funded by the Ministry of Science and ICT, Republic of Korea, and the NRF grant funded by the Korean government (NRF- 2017R1A5A1015365).
Funding Information:
This work is supported by “Next Generation Carbon Upcycling Project” (Project 2017M1A2A2046740) through the National Research Foundation (NRF) funded by the Ministry of Science and ICT, Republic of Korea, and the NRF grant funded by the Korean government (NRF-2017R1A5A1015365).
Publisher Copyright:
©
PY - 2020/11/11
Y1 - 2020/11/11
N2 - The efficient and selective light-driven conversion of carbon dioxide to formate is a scientific challenge for green chemistry and energy science, especially utilizing visible-light energy and earth-abundant catalytic materials. In this report, two mononuclear Ni(II) complexes of pyridylbenzimidazole (pbi) and pyridylbenzothiazole (pbt), such as Ni(pbt)(pyS)2 (1) and Ni(pbi)(pyS)2 (2) (pyS = pyridine-2-thiolate), were prepared and their reactivities studied. The two Ni complexes were examined for CO2 conversion using eosin Y as a photosensitizer upon visible-light irradiation in a H2O/ethanol solvent. The photoreaction of CO2 catalyzed by complexes 1 and 2 selectively affords formate with a high efficiency (14 000 turnover number) and a high catalytic selectivity of 99%. Undesirable proton reduction pathways were completely suppressed in the photocatalytic reactions with these sulfur-rich Ni catalysts under CO2. Hydrogen photoproduction was also studied under argon. Their kinetic isotope effects and influence of solution pH for formate and H2 production in the photocatalytic reactions are described in relation to the reaction mechanisms. These bioinspired Ni(II) catalysts with N/S ligation in relation to [NiFe]-hydrogenases are the first examples of early transition metal complexes affording such high selectivity and efficiencies, providing a future path to design solar-to-fuel processes for artificial photosynthesis.
AB - The efficient and selective light-driven conversion of carbon dioxide to formate is a scientific challenge for green chemistry and energy science, especially utilizing visible-light energy and earth-abundant catalytic materials. In this report, two mononuclear Ni(II) complexes of pyridylbenzimidazole (pbi) and pyridylbenzothiazole (pbt), such as Ni(pbt)(pyS)2 (1) and Ni(pbi)(pyS)2 (2) (pyS = pyridine-2-thiolate), were prepared and their reactivities studied. The two Ni complexes were examined for CO2 conversion using eosin Y as a photosensitizer upon visible-light irradiation in a H2O/ethanol solvent. The photoreaction of CO2 catalyzed by complexes 1 and 2 selectively affords formate with a high efficiency (14 000 turnover number) and a high catalytic selectivity of 99%. Undesirable proton reduction pathways were completely suppressed in the photocatalytic reactions with these sulfur-rich Ni catalysts under CO2. Hydrogen photoproduction was also studied under argon. Their kinetic isotope effects and influence of solution pH for formate and H2 production in the photocatalytic reactions are described in relation to the reaction mechanisms. These bioinspired Ni(II) catalysts with N/S ligation in relation to [NiFe]-hydrogenases are the first examples of early transition metal complexes affording such high selectivity and efficiencies, providing a future path to design solar-to-fuel processes for artificial photosynthesis.
UR - http://www.scopus.com/inward/record.url?scp=85096079888&partnerID=8YFLogxK
U2 - 10.1021/jacs.0c08145
DO - 10.1021/jacs.0c08145
M3 - Article
C2 - 33074684
AN - SCOPUS:85096079888
SN - 0002-7863
VL - 142
SP - 19142
EP - 19149
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 45
ER -