PMID- 32110360
OWN - NLM
STAT- PubMed-not-MEDLINE
LR  - 20200928
IS  - 2041-6520 (Print)
IS  - 2041-6539 (Electronic)
IS  - 2041-6520 (Linking)
VI  - 11
IP  - 1
DP  - 2020 Jan 7
TI  - Significantly improved electrocatalytic oxygen reduction by an asymmetrical 
      Pacman dinuclear cobalt(ii) porphyrin-porphyrin dyad.
PG  - 87-96
LID - 10.1039/c9sc05041h [doi]
AB  - Pacman dinuclear Co(II) triphenylporphyrin-tri(pentafluorophenyl)porphyrin 1 and 
      dinuclear Co(II) bis-tri(pentafluorophenyl)porphyrin 2, anchored at the two 
      meso-positions of a benzene linker, are synthesized and examined as 
      electrocatalysts for the oxygen reduction reaction (ORR). Both dinuclear Co 
      bisporphyrins are more efficient and selective than corresponding mononuclear 
      Co(II) tetra(pentafluorophenyl)porphyrin 3 and Co(II) tetraphenylporphyrin 4 for 
      the four-electron electrocatalytic reduction of O(2) to water. Significantly, 
      although the ORR selectivities of the two dinuclear Co bisporphyrins are similar 
      to each other, 1 outperforms 2, in terms of larger catalytic ORR currents and 
      lower overpotentials. Electrochemical studies showed different redox behaviors of 
      the two Co sites of 1: the Co(III)/Co(II) reduction of the Co-TPP (TPP = 
      triphenylporphyrin) site is well-behind that of the Co-TPFP (TPFP = 
      tri(pentafluorophenyl)porphyrin) site by 440 mV. This difference indicated their 
      different roles in the ORR: Co(II)-TPFP is likely the O(2) binding and reduction 
      site, while Co(III)-TPP, which is generated by the oxidation of Co(II)-TPP on 
      electrodes, may function as a Lewis acid to assist the O(2) binding and 
      activation. The positively charged Co(III)-TPP will have through-space charge 
      interactions with the negatively charged O(2)-adduct unit, which will reduce the 
      activation energy barrier for the ORR. This effect of Co-TPP closely resembles 
      that of the Cu(B) site of metalloenzyme cytochrome c oxidase (CcO), which 
      catalyzes the biological reduction of O(2). This work represents a rare example 
      of asymmetrical dinuclear metal catalysts, which can catalyze the 4e reduction of 
      O(2) with high selectivity and significantly improved activity.
CI  - This journal is (c) The Royal Society of Chemistry 2020.
FAU - Liu, Yanju
AU  - Liu Y
AD  - Key Laboratory of Applied Surface and Colloid Chemistry , Ministry of Education , 
      School of Chemistry and Chemical Engineering , Shaanxi Normal University , Xi'an 
      710119 , China . Email: ruicao@ruc.edu.cn.
AD  - Department of Chemistry , Renmin University of China , Beijing 100872 , China.
FAU - Zhou, Guojun
AU  - Zhou G
AD  - Key Laboratory of Applied Surface and Colloid Chemistry , Ministry of Education , 
      School of Chemistry and Chemical Engineering , Shaanxi Normal University , Xi'an 
      710119 , China . Email: ruicao@ruc.edu.cn.
FAU - Zhang, Zongyao
AU  - Zhang Z
AD  - Department of Chemistry , Renmin University of China , Beijing 100872 , China.
FAU - Lei, Haitao
AU  - Lei H
AD  - Key Laboratory of Applied Surface and Colloid Chemistry , Ministry of Education , 
      School of Chemistry and Chemical Engineering , Shaanxi Normal University , Xi'an 
      710119 , China . Email: ruicao@ruc.edu.cn.
FAU - Yao, Zhen
AU  - Yao Z
AUID- ORCID: 0000-0003-0010-913X
AD  - College of Materials Science and Optoelectronic Technology , University of 
      Chinese Academy of Science , Beijing 101408 , China.
FAU - Li, Jianfeng
AU  - Li J
AUID- ORCID: 0000-0002-4876-8970
AD  - College of Materials Science and Optoelectronic Technology , University of 
      Chinese Academy of Science , Beijing 101408 , China.
FAU - Lin, Jun
AU  - Lin J
AUID- ORCID: 0000-0001-8075-6091
AD  - Department of Chemistry , Renmin University of China , Beijing 100872 , China.
FAU - Cao, Rui
AU  - Cao R
AUID- ORCID: 0000-0002-1821-9583
AD  - Key Laboratory of Applied Surface and Colloid Chemistry , Ministry of Education , 
      School of Chemistry and Chemical Engineering , Shaanxi Normal University , Xi'an 
      710119 , China . Email: ruicao@ruc.edu.cn.
LA  - eng
PT  - Journal Article
DEP - 20191104
PL  - England
TA  - Chem Sci
JT  - Chemical science
JID - 101545951
PMC - PMC7012046
EDAT- 2020/02/29 06:00
MHDA- 2020/02/29 06:01
PMCR- 2019/11/04
CRDT- 2020/02/29 06:00
PHST- 2019/10/07 00:00 [received]
PHST- 2019/11/03 00:00 [accepted]
PHST- 2020/02/29 06:00 [entrez]
PHST- 2020/02/29 06:00 [pubmed]
PHST- 2020/02/29 06:01 [medline]
PHST- 2019/11/04 00:00 [pmc-release]
AID - c9sc05041h [pii]
AID - 10.1039/c9sc05041h [doi]
PST - epublish
SO  - Chem Sci. 2019 Nov 4;11(1):87-96. doi: 10.1039/c9sc05041h. eCollection 2020 Jan 
      7.