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Updated: Jul 11, 2025

Synthesis of Hypervalent Iodonium Alkynyl Triflates for the Application of Generating Cyanocarbenes
Published on: September 8, 2013
Tetraiodo Fe/Ni phthalocyanine-based molecular catalysts for highly efficient oxygen reduction reaction and oxygen
Jingshun Shen1, Qi Liu1, Yuexing Zhang2
1School of Materials Science and Engineering, China University of Petroleum (East China), Qingdao 266580, PR China.
Abstract:
In this paper, we report on the preparation and catalysis of a bifunctional molecular catalyst (Fe[Pc(I)4]+Ni[Pc(I)4]@NCPDI) for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in rechargeable Zn-air batteries. This catalyst is prepared by self-assembling tetraiodo metal phthalocyanines (Fe[Pc(I)4] and Ni[Pc(I)4]) on a 2D N-doped carbon material (NCPDI) through π-π interactions. The introduction of iodine groups in the edge of phthalocyanines controls the density of electron cloud and electrostatic potential around Fe-N/Ni-N sites and constructs a built-in electric field that facilitates directional transport of charges, enhancing the catalytic activity of the catalyst. Density functional theory (DFT) calculations support this mechanism by showing a reduced energy barrier for the ORR rate-determining step (RDS). The Fe[Pc(I)4]+Ni[Pc(I)4]@NCPDI exhibits excellent performance outperforming 20 wt% Pt/C and single-molecule self-assembled Fe[Pc(I)4]@NCPDI and Ni[Pc(I)4]@NCPDI, with a half-wave potential of E1/2 = 0.940 V in the ORR process under alkaline condition. During the OER process, Fe[Pc(I)4]+Ni[Pc(I)4]@NCPDI exhibited a low overpotential of 298 mV at 10 mA cm-2 under the alkaline condition, which is much better than RuO2, Fe[Pc(I)4]@NCPDI and Ni[Pc(I)4]@NCPDI. The catalyst also demonstrates excellent catalysis and durability in rechargeable Zn-air batteries. This work provides a simple and specific method to develop efficient multifunctional molecular electrocatalysts.
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