Metal–Organophosphine Framework‐Derived N,P‐Codoped Carbon‐Confined Cu3P Nanopaticles for Superb Na‐Ion Storage

Metal–organic framework derived approaches are emerging as a viable way to design carbon‐confined transitional metal phosphides (TMPs@C) for energy storage and conversion. However, their preparation generally involves a phosphorization using a large amount of additional P sources, which inevitably releases flammable, poisonous PH₃. Therefore, developing an efficient strategy for eco‐friendly synthesis of TMPs@C is full of challenges. Here, a metal–organophosphine framework (MOPF) derived strategy is developed to allow an eco‐friendly design of TMPs@C without an additional P source, avoiding release of PH₃. To illustrate this strategy, 1,3,5‐triaza‐7‐phosphaadamantane (PTA) ligands and Cu(NO₃)₂ metal centers are employed to construct Cu/PTA‐MOPFs nanosheets. Cu/PTA‐MOPFs can be directly converted to carbon‐confined Cu₃P nanoparticles by annealing. Benefiting from high heteroatom content in PTA, a high doping content of 3.92 at% N and 8.26 at% P can also be achieved in the carbon matrix. As a proof‐of‐concept application, N,P‐codoped carbon‐confined Cu₃P nanoparticles as anodes for Na‐ion storage exhibit a high initial reversible capacity of 332 mA h g^?1 at 50 mA g^?1, and superb rate and cyclic performance. Due to rich coordination modes of organophosphine, MOPFs are expected to become a promising molecular platform for design of various heteroatom‐doped TMPs@C for energy storage and conversion.