Porous Organic Polymers‐Based Single‐Atom Catalysts for Sustainable Energy‐Related Electrocatalysis

Abstract

Single‐atom catalysts (SACs) have been emerging as attractive catalytic materials in electrocatalysis for sustainable energy storage and conversion. To realize the practical implementation of SACs, reliable support is highly imperative to stabilize atomically dispersed metals with strong metal–support interaction, tunable local electronic environment, and favorable electron/mass transport. Thanks to great designability and tunability of composition, structure, and morphology, porous organic polymers (POPs) have demonstrated grand promise as appropriate support platforms toward the design of SACs at the molecular level and the fabrication of SACs in a controlled manner. Herein, a comprehensive overview of recent advances toward the elucidation of general design principles, effective synthesis approaches, and fundamental catalytic mechanisms for boosting the development of high‐performance POPs‐based SACs in electrocatalytic transformations is provided. The authors first outline rationales for using POPs‐based supports to stabilize SACs and design principles for electrocatalysis, followed by discussing fabrication approaches of utilizing POPs and POPs‐derived nanocarbons to host single‐atom metals. Then, state‐of‐the‐art POPs‐based SACs and their applications in heterogeneous electrocatalysis (ORR, OER, HER, CO2RR, and NRR) are discussed, of which the focus is on revealing the structure–performance correlation and catalytic mechanisms. Finally, challenges and strategies associated with the rational design of high‐performance SACs are suggested.

N and OH-Immobilized Cu3 Clusters In Situ Reconstructed from Single-Metal Sites for Efficient CO2 Electromethanation in Bicontinuous Mesochannels

“…In contrast, the position of other N species remained unchanged. This observation suggests that the stabilization of single Cu metals involves strong coordination with pyridinic N, forming Cu–N bonds due to the existence of lone-pair electrons on pyridinic N. − …”

Mechanosynthesis of a bifunctional FeNi–N–C oxygen electrocatalyst via facile mixed-phase templating and preheating-pyrolysis

“…28,29 Therefore, in recent studies, mechanosynthesis has been employed as an effective and greener alternative for conventional solvent-based synthesis to reduce or eliminate the generation of waste and material and energy overuse. 30–33 The mechanochemical synthesis is performed in a solid phase where mechanical energy is transferred to reactants by grinding with minimal or no solvent. 34–36 Furthermore, to advance the solid-phase synthesis of M–N-Cs, templating with cheap and abundant inorganics is employed to boost the catalytic performance and production efficiency.…”

Single-Atom Catalysts on Covalent Organic Frameworks for Energy Applications

“…1,19 To disperse metals atomically homogeneously and achieve the best possible efficiency from such an arrangement, one strategy is to confine and stabilize the metal atoms in substrate skeletons with atomic-scale precision. For these purposes, substrates have been widely investigated, including metal oxides, 1,13 graphene, 20,21 porous polymers, 22,23 metal−organic frameworks (MOFs), 24,25 covalent organic frameworks (COFs), 19,26 etc.…”