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Enhanced Four‐Electron Selective Oxygen Reduction Reaction at Carbon‐Nanotube‐Supported Sulfonic‐Acid‐Functionalized Copper Phthalocyanine

Von Wiley-VCH zur Verfügung gestellt

Nitrogen-doped multi-walled carbon nanotubes (NMWCNTs) are synthesized. Further, sulfonic-acid-functionalized copper phthalocyanine (CuPc-SO3 ) is integrated into the NMWCNTs (NMWCNTs-CuPc-SO3 ) and characterized. The NMWCNT-CuPc-SO3 material is highly selective towards the four-electron oxygen reduction reaction at low overpotentials, as determined by rotating ring electrode studies.


In the present work, the oxygen reduction reaction (ORR) is explored in an acidic medium with two different catalytic supports (multi-walled carbon nanotubes (MWCNTs) and nitrogen-doped multi-walled carbon nanotubes (NMWCNTs)) and two different catalysts (copper phthalocyanine (CuPc) and sulfonic acid functionalized CuPc (CuPc-SO3 )). The composite, NMWCNTs-CuPc-SO3 exhibits high ORR activity (assessed based on the onset potential (0.57 V vs. reversible hydrogen electrode) and Tafel slope) in comparison to the other composites. Rotating ring disc electrode (RRDE) studies demonstrate a highly selective four-electron ORR (less than 2.5 % H2O2 formation) at the NMWCNTs-CuPc-SO3 . The synergistic effect of the catalyst support (NMWCNTs) and sulfonic acid functionalization of the catalyst (in CuPc-SO3 ) increase the efficiency and selectivity of the ORR at the NMWCNTs-CuPc-SO3 . The catalyst activity of NMWCNTs-CuPc-SO3 has been compared with many reported materials and found to be better than several catalysts. NMWCNTs-CuPc-SO3 shows high tolerance for methanol and very small deviation in the onset potential (10 mV) between the linear sweep voltammetry responses recorded before and after 3000 cyclic voltammetry cycles, demonstrating exceptional durability. The high durability is attributed to the stabilization of CuPc-SO3 by the additional coordination with nitrogen (Cu-Nx) present on the surface of NMWCNTs.

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