Highly Efficient Catalytic Two-Electron Two-Proton Reduction of Dioxygen to Hydrogen Peroxide with a Cobalt Corrole Complex
- 주제(키워드) selective O-2 reduction , cobalt corrole , H2O2 production , reaction mechanism , efficient catalysis
- 주제(기타) Chemistry, Physical
- 설명문(일반) [Rana, Atanu; Lee, Yong-Min; Fukuzumi, Shunichi; Nam, Wonwoo] Ewha Womans Univ, Dept Chem & Nano Sci, Seoul 03760, South Korea; [Li, Xialiang; Cao, Rui; Nam, Wonwoo] Shaanxi Normal Univ, Sch Chem & Chem Engn, Key Lab Appl Surface & Colloid Chem, Minist Educ, Xian 710119, Peoples R China; [Fukuzumi, Shunichi] Meijo Univ, Fac Sci & Engn, Nagoya, Aichi 4688502, Japan
- 등재 SCIE, SCOPUS
- 발행기관 AMER CHEMICAL SOC
- 발행년도 2021
- 총서유형 Journal
- URI http://www.dcollection.net/handler/ewha/000000181491
- 본문언어 영어
- Published As http://dx.doi.org/10.1021/acscatal.0c05003
초록/요약
Selective and efficient catalytic two-electron two-proton (2e(-)/2H(+)) reduction of dioxygen (O-2) to hydrogen peroxide (H2O2) has been achieved less successfully than four-electron four-proton (4e(-)/4H(+)) reduction of O-2 because of the instability of the H2O2 product in the presence of metal catalysts. We report herein a highly efficient 2e(-)/2H(+) reduction of O-2 by ferrocene (Fc; one-electron reductant) and 9,10-dihydro-10-methylacridine (AcrH(2); two-electron reductant and an NADH analog), with a cobalt corrole complex, [Co-III(tpfc)(Py)(2)] (1), in the presence of HClO4 in CH3CN at 298 K, affording a large TON (50,000) and a high turnover frequency (275 s(-1)) with 100% selectivity in producing H2O2. The H2O2 product yielded in the 2e(-)/2H(+) reduction of O-2 using AcrH(2) as a reductant was stable for more than 5 h even in the presence of 1. Detailed kinetic analysis revealed that the rate-determining step (rds) for the 2e(-)/2H(+) reduction of O-2 by Fc with 1 in the presence of HClO4 in CH3CN was the proton-coupled electron transfer from Co-III(tpfc) (2) to O-2 to produce a cobalt(III) corrole radical cation, [CoIII(tpfc(+))](+) (3), which was detected by EPR. When ferrocene was replaced by AcrH(2), the rds became the electron transfer from AcrH(2) to 3, coupled with the deprotonation of AcrH(2)(center dot+) (ET/PT), followed by fast ET from AcrH(center dot) to 3. To the best of our knowledge, this is a report of a highly efficient Co-corrole catalyst that retains its cobalt(III) oxidation state for the 2e(-)/2H(+) reduction of O-2 in producing H2O2 with a high selectivity.
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