Issue 34, 2023

Cofacial porphyrin organic cages. Metals regulating excitation electron transfer and CO2 reduction electrocatalytic properties

Abstract

Herein, we introduce a comprehensive study of the photophysical behaviors and CO2 reduction electrocatalytic properties of a series of cofacial porphyrin organic cages (CPOC-M, M = H2, Co(II), Ni(II), Cu(II), Zn(II)), which are constructed by the covalent-bonded self-assembly of 5,10,15,20-tetrakis(4-formylphenyl)porphyrin (TFPP) and chiral (2-aminocyclohexyl)-1,4,5,8-naphthalenetetraformyl diimide (ANDI), followed by post-synthetic metalation. Electronic coupling between the TFPP donor and naphthalene-1,4 : 5,8-bis(dicarboximide) (NDI) acceptor in the metal-free cage is revealed to be very weak by UV-vis spectroscopic, electrochemical, and theoretical investigations. Photoexcitation of CPOC-H2, as well as its post-synthetic Zn and Co counterparts, leads to fast energy transfer from the triplet state porphyrin to the NDI unit according to the femtosecond transient absorption spectroscopic results. In addition, CPOC-Co enables much better electrocatalytic activity for CO2 reduction reaction than the other metallic CPOC-M (M = Ni(II), Cu(II), Zn(II)) and monomeric porphyrin cobalt compartment, supplying a partial current density of 18.0 mA cm−2 at −0.90 V with 90% faradaic efficiency of CO.

Graphical abstract: Cofacial porphyrin organic cages. Metals regulating excitation electron transfer and CO2 reduction electrocatalytic properties

Supplementary files

Article information

Article type
Edge Article
Submitted
09 Apr 2023
Accepted
28 Jul 2023
First published
10 Aug 2023
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2023,14, 9086-9094

Cofacial porphyrin organic cages. Metals regulating excitation electron transfer and CO2 reduction electrocatalytic properties

X. Liu, C. Liu, X. Song, X. Ding, H. Wang, B. Yu, H. Liu, B. Han, X. Li and J. Jiang, Chem. Sci., 2023, 14, 9086 DOI: 10.1039/D3SC01816D

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