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.

as N, B, O, S, and P, has been regarded as one of the most effective methods to boost the Na-ion storage in carbons by creating additional active sites and modifying the electronic structure of carbon. [6] Compared with nonmetal doping, doping of single atomic metal (SAM) is expected to exhibit more promising properties. Theoretical studies have shown that SAM dopants in graphene, such as Be-doped graphene, [7] Be,N dual-doped graphene, [8] and Si,Gecodoped graphene, [9] can enhance diffusion kinetics and provide anchoring sites for alkali metal-ions. SAM doping results in more delocalized electrons than nonmetal doping, enhancing electron conductivity. Additionally, SAMs render stronger affinity and lower migration resistance of alkali metal-ions in carbons. [10] Recent reports show that carbon-supported SAMs not only are being intensively investigated in electrocatalysts, [11] but also arouse great interests in Li-metal batteries [12] and Na-S batteries. [13] However, there is still no experimental investigation about the influence of SAMs on the Na-ion storage as well as other alkali metal-ion storage.Novel methods, such as atomic layer loading, chemical vapor deposition, wet chemistry route, and high-energy ball milling strategy, have been developed to prepare SAM-doped carbons, but they suffer from high cost and low yield. [11,14] Compared with these methods, metal-organic frameworks (MOFs)-derived strategy have gained tremendous popularity to construct carbonsupported SAMs. This method generally involves preparation of MOFs and subsequent pyrolysis. During pyrolysis, metal is exceedingly vulnerable to aggregate, [15] so maintaining single atomic state is a major challenge. Many strategies have been adopted to inhibit metal aggregation such as Zn-evaporation, [16][17][18][19][20][21][22] trapping of uncoordinated groups, [23][24][25] etc. Basic ideas for these methods are to increase the distance between metal atoms and/ or strengthen the interaction between metal and anchoring sites to avoid aggregation. Nevertheless, achieving high content doping of SAMs in MOFs-derived carbon is still a great challenge. [26][27][28][29] Low loading-content severely hinders its practical use in current application fields [11][12][13] and also blocks its expansion in other fields such as SIBs. It is urgent to explore novel MOF-derived stategies to realize high-loading SAMs.Achieving high-content loading of SAMs necessitates enhancing metal-ligand interaction. The MOF precursors for Carbon-supported single atomic metals (SAMs) have aroused great interest in energy conversion and storage fields. However, metal content has to date, been far below expectation. Additionally, theoretical calculations show that SAMs are superb anchoring sites for alkali metal-ion storage, but the experimental research remains untouched. Herein, a metal-organophosphine framework derived strategy is proposed to prepare carbon microcuboidssupported single atomic Cu with a high content of 26.3 wt%. Atomic Cu is stabilized mainly by P moieties, exhibit...

Perovskite framework NH4FeF3/CNS composites were prepared by an in situ co-pyrolysis method and exhibit better performance as anodes for both LIBs and SIBs.