Supramolecularly Built Local Electric Field Microenvironment around Cobalt Phthalocyanine in Covalent Organic Frameworks for Enhanced Photocatalysis

The local electric field (LEF) plays an important role in the catalytic process; however, the precise construction and manipulation of the electric field microenvironment around the active site remains a significant challenge. Here, we have developed a supramolecular strategy for the implementation of a LEF by introducing the host macrocycle 18-crown-6 (18C6) into a cobalt phthalocyanine (CoPc)-containing covalent organic framework (COF). Utilizing the supramolecular interaction between 18C6 and potassium ion (K+), a locally enhanced K+ concentration around CoPc can be built to generate a LEF microenvironment around the catalytically active Co site. The COF with this supramolecularly built LEF realizes an activity of up to 7.79 mmol mmolCo–1 h–1 in the photocatalytic CO2 reduction reaction (CO2RR), which is a 180% improvement compared to its counterpart without 18C6 units. The effect of LEF can be subtly controlled by fully harnessing the K+@18C6 interaction by changing the potassium salts with different counterions. In situ spectroscopy and density functional theory calculations show that the complexation of K+ by 18C6 creates a positive electric field that stabilizes the critical intermediate *COOH involved in CO2RR, which can be tuned by the halide ion-mediated K+@18C6 interaction and hydrogen-bonding interaction, consequently leading to improved catalytic performance to varying degrees.