A Phthalocyanine‐Based Layered Two‐Dimensional Conjugated Metal–Organic Framework as a Highly Efficient Electrocatalyst for the Oxygen Reduction Reaction. (1st July 2019)

• Record Type: Journal Article
• Authors: 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
• Is Part Of: Angewandte Chemie. Volume 131:Number 31(2019)
• Page Start: 10787
• Page End: 10792
• Publication Date: 2019-07-01
• Subjects: Elektrokatalysatoren -- Katalytische Zentren -- Metall-organische Gerüste -- Sauerstoffreduktionsreaktion; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201907002
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: 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‐O4 ) as linkages (PcCu‐O8 ‐Co) and layer‐stacked structures prepared via solvothermal synthesis. PcCu‐O8 ‐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‐O8 ‐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 ). Abstract : Gut verbunden : Ein Kupferphthalocyanin‐basiertes 2D‐konjugiertes MOF mit quadratisch‐planaren Cobalt‐bis(dihydroxy)‐Einheiten (Co‐O4) als Verbindungsstellen kann mit hoher katalytischer Aktivität als Elektrokatalysator für die Sauerstoffreduktionsreaktion genutzt werden ( E 1/2 =0.83 V vs. RHE). Die verknüpfenden Co‐Zentren mit optimierter elektronischer Struktur (eg =1) stellen dabei die aktiven Zentren dar.