Rational design and synthesis of two-dimensional conjugated metal-organic polymers for electrocatalysis applications

The bigger pictureElectrocatalytic energy conversion technology is widely regarded as an important way to reduce carbon emissions and achieve carbon neutrality. Electrocatalysts are essential to reducing reaction kinetic barriers and improving the catalytic reaction efficiency. 2D conjugated metal-organic polymers (c-MOPs) have shown promising prospects as electrocatalysts owing to their versatile structures, large surface areas, tailorable pore-sizes, and high conductivity. The mechanism of c-MOPs in electrocatalysis has not yet been fully understood and systematically summarized.This review summarized the recent key advances of 2D c-MOPs in design principles, conductive mechanism, crystal structure, synthesized methods, and applications in electrochemical catalysis. An in-depth summary and understanding of the design principles and catalytic performance of c-MOPs, also established in this review, provides guidance for c-MOP development and an understanding of the electrocatalytic mechanism.SummaryTwo-dimensional (2D) conjugated metal-organic polymers (c-MOPs), an emerging family of 2D materials, have attracted widespread interest for application in electrocatalysis due to their flexibly tunable components, abundance of accessible active sites, and high conductivity. The key challenges facing the usage of 2D c-MOPs as electrocatalysts are the need for rational design and synthesis methods for coordination polymers as well as an in-depth understanding of structure-activity relationships. Herein, we summarize the design principles, synthesis methods, conductive mechanisms, and catalytic behaviors of 2D c-MOPs. The large d-π conjugation network and strong π-π stacking are responsible for the high conductivity of 2D c-MOPs. The coordination environment and electronic configuration of metal centers are decisive factors affecting the catalytic properties of 2D c-MOPs. This review provides insights into the preparation of 2D conductive c-MOP materials via modulation and optimization of active sites to enable high performance in electrochemical energy conversion systems.Graphical abstract