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

Abstract

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.

Vertical CoP Nanoarray Wrapped by N,P‐Doped Carbon for Hydrogen Evolution Reaction in Both Acidic and Alkaline Conditions

“…[42] For the highresolution N 1s XPS spectra, three peaks at 399.3, 400.2, and 401.5 eV correspond to the BE of pyridinic N, pyrrodic N, and graphitic N, respectively, which also confirm the successful formation of N-doped carbon. [43] Note that XPS spectra indicate that N and P atoms are not bonded to form any PN species. [44] According to XPS data, CoP/NPC/TF consists of Co (19.80%), P (22.15%), C (39.52%), N (6.31%), and O (12.22%) (Table S1, Supporting Information).…”

Carbon‐Microcuboid‐Supported Phosphorus‐Coordinated Single Atomic Copper with Ultrahigh Content and Its Abnormal Modification to Na Storage Behaviors

“…Then the cuboids with 3D superamolecular framework are assembled by coordination units via hydrogen bonds. [ 33–36 ] According to elemental analysis (Table S1, Supporting Information), the molecular formula of the MOPF cuboids should be denoted as [Cu(PTA) 3 (PTAH)](NO 3 ) 2 ·2H 2 O.…”

“…[ 40 ] The peak at 130.7 eV should be assigned to CuP bond. [ 33 ] Therefore, Cu atoms should be stabilized by CuP bond and CuOP bond, respectively. The P2p spectrum (Figure S10b, Supporting Information) of CUB‐600‐HCl shows that the peak for PO/CuOP at 133.5 eV is obviously decreased.…”

Virus‐Templated Nickel Phosphide Nanofoams as Additive‐Free, Thin‐Film Li‐Ion Microbattery Anodes

“…Over the last several decades, several classes of materials have emerged as possible conversion anodes for both micro-and macrobatteries, such as transition metal oxides, [10] carbides, [11] and sulfides. [12] In particular, metal phosphides have displayed strong performance in both lithium-ion [13][14][15] and sodium-ion [16][17][18][19] batteries, owing to their high capacity, good electronic conductivity, and naturally abundant constituent elements.Despite their technological promise, synthesis of metal phosphides has traditionally been challenging due to the flammability and toxicity of common phosphoruscontaining precursors. [20] Simultaneous control over nanostructure, crystal structure, and surface morphology remains imprecise, thereby impeding electrode design and incorporation into devices.…”