Visible-Light Photocatalytic Conversion of Carbon Dioxide by Ni(II) Complexes with N4S2 Coordination: Highly Efficient and Selective Production of Formate
- 주제(기타) Chemistry, Multidisciplinary
- 설명문(일반) [Lee, Sung Eun; Nasirian, Azam; Kim, Ye Eun; Fard, Pegah Tavakoli; Kim, Youngmee; Jeong, Byeongmoon; Kim, Sung-Jin; Kim, Jinheung] Ewha Womans Univ, Dept Chem & Nano Sci, Seoul 03760, South Korea; [Baeg, Jin-Ook] Korea Res Inst Chem Technol KRICT, Adv Chem Technol Div, Daejeon 34114, South Korea
- 등재 SCIE, SCOPUS
- 발행기관 AMER CHEMICAL SOC
- 발행년도 2020
- 총서유형 Journal
- URI http://www.dcollection.net/handler/ewha/000000175432
- 본문언어 영어
- Published As http://dx.doi.org/10.1021/jacs.0c08145
- PubMed https://pubmed.ncbi.nlm.nih.gov/33074684
초록/요약
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 (14000 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 H-2 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.
more