Metal‐Phosphide‐Containing Porous Carbons Derived from an Ionic‐Polymer Framework and Applied as Highly Efficient Electrochemical Catalysts for Water Splitting

Abstract

A novel phosphorus‐containing porous polymer is efficiently prepared from tris(4‐vinylphenyl)phosphane by radical polymerization, and it can be easily ionized to form an ionic porous polymer after treatment with hydrogen iodide. Upon ionic exchange, transition‐metal‐containing anions, such as tetrathiomolybdate (MoS4 2−) and hexacyanoferrate (Fe(CN)6 3−), are successfully loaded into the framework of the porous polymer to replace the original iodide anions, resulting in a polymer framework containing complex anions (termed HT‐Met, where Met = Mo or Fe). After pyrolysis under a hydrogen atmosphere, the HT‐Met materials are efficiently converted at a large scale to metal‐phosphide‐containing porous carbons (denoted as MetP@PC, where again Met = Mo or Fe). This approach provides a convenient pathway to the controlled preparation of metal‐phosphide‐loaded porous carbon composites. The MetP@PC composites exhibit superior electrocatalytic activity for the hydrogen evolution reaction (HER) under acidic conditions. In particular, MoP@PC with a low loading of 0.24 mg cm−2 (on a glass carbon electrode) affords an iR‐corrected (where i is current and R is resistance) current density of up to 10 mA cm−2 at 51 mV versus the reversible hydrogen electrode and a very low Tafel slope of 45 mV dec−1, in rotating disk measurements under saturated N2 conditions.

Tunable and Specific Formation of C@NiCoP Peapods with Enhanced HER Activity and Lithium Storage Performance

“…The measured Ta fel slope for Pt/ C, C@Ni 2 P, C@Ni 1.5 Co 0.5 P, C@NiCoP,a nd Co 2 Pb ulk is 30, 74, 50, 43, and 120 mV dec ,r espectively;t hesed ata are in the range reported by previous studies on non-precious-metal HER catalysts. [37][38][39] To furthera ssess the intrinsic activityo ft he as-prepared catalyst, the exchange current density was calculated by extrapolating the Tafel plot. It was noted that the peapodlike C@NiCoP shows an exchange current density of as high as 0.21 mA cm…”

3D Nanoporous Metal Phosphides toward High‐Efficiency Electrochemical Hydrogen Production

“…[15][16][17][18][19] Especially, nanostructured cobalt phosphides show exceptionally high activity toward hydrogen evolution reaction (HER). [ 16,17 ] Currently, the nanostructured metal phosphides are mainly synthesized by solvothermal methods [ 16,18 ] and phosphidation of nanostructured transition metal oxides/hydroxides, [ 17,20,21 ] which often suffer from inevitable environmental pollutions from phosphorization process, less electrochemical stability from the inadequate contact with conductive supports and binders, and low energy effi ciency from high internal resistance.…”

Trends and challenges for microporous polymers

“…Recently Zhuang et al have synthesized a porous non-ionic phosphine network through radical polymerization with AIBN. 195 The network was then charged by generating phosphonium species through protonation of the phosphine moieties. Solid state 31 P-NMR spectroscopy confirmed the completion of conversion and total lack of residual phosphine species.…”