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A Phthalocyanine‐Based Layered Two‐Dimensional Conjugated Metal–Organic Framework as a Highly Efficient Electrocatalyst for the Oxygen Reduction Reaction
Author(s) -
Zhong Haixia,
Ly Khoa Hoang,
Wang Mingchao,
Krupskaya Yulia,
Han Xiaocang,
Zhang Jichao,
Zhang Jian,
Kataev Vladislav,
Büchner Bernd,
Weidinger Inez M.,
Kaskel Stefan,
Liu Pan,
Chen Mingwei,
Dong Renhao,
Feng Xinliang
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201907002
Subject(s) - electrocatalyst , phthalocyanine , cobalt , electrochemistry , metal organic framework , catalysis , conjugated system , materials science , metal , raman spectroscopy , inorganic chemistry , chemistry , chemical engineering , nanotechnology , organic chemistry , electrode , polymer , physics , adsorption , engineering , optics
Layered two‐dimensional (2D) conjugated metal–organic frameworks (MOFs) represent a family of rising electrocatalysts for the oxygen reduction reaction (ORR), due to the controllable architectures, excellent electrical conductivity, and highly exposed well‐defined molecular active sites. Herein, we report a copper phthalocyanine based 2D conjugated MOF with square‐planar cobalt bis(dihydroxy) complexes (Co‐O 4 ) as linkages (PcCu‐O 8 ‐Co) and layer‐stacked structures prepared via solvothermal synthesis. PcCu‐O 8 ‐Co 2D MOF mixed with carbon nanotubes exhibits excellent electrocatalytic ORR activity ( E 1/2 =0.83 V vs. RHE, n =3.93, and j L =5.3 mA cm −2 ) in alkaline media, which is the record value among the reported intrinsic MOF electrocatalysts. Supported by in situ Raman spectro‐electrochemistry and theoretical modeling as well as contrast catalytic tests, we identified the cobalt nodes as ORR active sites. Furthermore, when employed as a cathode electrocatalyst for zinc–air batteries, PcCu‐O 8 ‐Co delivers a maximum power density of 94 mW cm −2 , outperforming the state‐of‐the‐art Pt/C electrocatalysts (78.3 mW cm −2 ).