Highly efficient electrocatalysts derived from metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) for oxygen reduction reaction (ORR) have been developed. However, the subsequent pyrolysis is often needed owing to their poor intrinsic electrical conductivity, leading to undesirable structure changes and destruction of the original fine structure. Now, hybrid electrocatalysts were formed by self-assembling pristine covalent organic polymer (COP) with reduced graphene oxide (rGO). The electrical conductivity of the hybridized COP/rGO materials is increased by more than seven orders of magnitude (from 3.06×10 to 2.56×10 S m ) compared with pure COPs. The ORR activities of the hybrid are enhanced significantly by the synergetic effect between highly active COP and highly conductive rGO. This COP/rGO hybrid catalyst exhibited a remarkable positive half-wave (150 mV).

Highly efficient electrocatalysts are vital to meet energy and environmental challenges. Although numerous nonprecious metal or metal-free carbon-based catalysts have been demonstrated to entirely or partially replace noble-metal-based electrocatalysis, the absence of precise design and a predictable process hindered the development. Well-defined 2D covalent organic polymers (COPs) as a new exciting type of electrocatalyst presented superior potentials with precisely controllable capacities, such as robust tailoring heteroatom incorporation and location of active sites. Here we demonstrate the possibilities and potential of the well-defined 2D COPs used as highly efficient energy electrocatalysts for clean and renewable energy technologies. After surveying recent developments, we further discuss the possible future directions for designed synthesis of intrinsic COPs without carbonization to modulate active sites and the density of active sites at the molecular level. COP materials as a new family of electrocatalysts offer practical possibilities to study the structure, mechanism, and kinetics of energy electrocatalysis and may lead to a better solution for energy and environmental issues.

The output energy capacity of green electrochemical devices, e.g., fuel cells, depends strongly on the sluggish oxygen reduction reaction (ORR), which requires catalysts. One of the desired features for highly efficient ORR electrocatalytic materials is the richness of well-defined activate sites. Herein, we developed a facile approach to prepare highly efficient nonprecious metal and nitrogen-doped carbon-based ORR catalysts based on covalent organic polymers (COPs) synthesized in situ in the nanoconfined space of highly ordered metal organic frameworks (MOFs). The MOF templet ensured the developed electrocatalysts possess a high surface area with homogeneously distributed small metal/nitrogen active sites, as confirmed by X-ray absorption fine structure measurements and first-principles calculations, leading to highly efficient ORR electrocatalytic activity. Notably, the developed COP-TPP(Fe)@MOF-900 exhibits a 16 mV positive half-wave potential compared with the benchmarked Pt/C.

Atomically dispersed transition metal‐Nx sites have emerged as a frontier for electrocatalysis because of the maximized atom utilization. However, there is still the problem that the reactant is difficult to reach active sites inside the catalytic layer in the practical proton exchange membrane fuel cell (PEMFC) testing, resulting in the ineffective utilization of the deeply hided active sites. In the device manner, the favorite structure of electrocatalysts for good mass transfer is vital for PEMFC. Herein, a facile one‐step approach to synthesize atomically dispersed Fe‐Nx species on hierarchically porous carbon nanostructures as a high‐efficient and stable atomically dispersed catalyst for oxygen reduction in acidic media is reported, which is achieved by a predesigned hierarchical covalent organic polymer (COP) with iron anchored. COP materials with well‐defined building blocks can stabilize the dopants and provide efficient mass transport. The appropriate hierarchical pore structure is proved to facilitate the mass transport of reactants to the active sites, ensuring the utilization of active sites in devices. Particularly, the structurally optimized HSAC/Fe‐3 displays a maximum power density of up to 824 mW cm−2, higher than other samples with fewer mesopores. Accordingly, this work will offer inspirations for designing efficient atomically dispersed electrocatalyst in PEMFC device.