Positional Thiophene Isomerization: A Geometric Strategy for Precisely Regulating the Electronic State of Covalent Organic Frameworks to Boost Oxygen Reduction

With the oxygen conversion efficiency of metal‐free carbon‐based fuel cells dramatically improved, the building blocks of covalent organic frameworks (COFs) raised principal concerns on the catalytic active sites with indistinct electronic states. Herein, to address this issue, we demonstrate COFs for oxygen reduction reaction (ORR) by regulating the edge‐hanging thiophene units, and the molecular geometries are further modulated via positional thiophene isomerization strategy, affording isomeric COF‐α with 2‐substitution and COF‐β with 3‐substitution on the frameworks. The electronic states and intermediate adsorption ability are well‐regulated through geometric modification, resulting in controllable chemical activity and local density of π‐electrons. Notably, the introduction of thiophene units with different substitution positions into a pristine pure carbon‐based COF model COF‐Ph achieves excellent activity with a half‐wave potential of 0.76 V versus the reversible hydrogen electrode, which is higher than most of those metal‐free or metal‐based electrocatalysts. Utilizing the combination of theoretical prediction and in situ Raman spectra, we show that the isomeric thiophene skeleton (COF‐α and COF‐β) can induce the dangling unit activation, accurately identifying the pentacyclic‐carbon (thiophene α‐position) adjacent to sulfur atom as active sites. The results suggest that the isomeric dangling groups in COFs are suitable for the ORR with suitable geometry construction.