Confined Molybdenum Phosphide in P-Doped Porous Carbon as Efficient Electrocatalysts for Hydrogen Evolution

Abstract

Highly efficient electrocatalysts for hydrogen evolution reactions (HER) are crucial for electrochemical water splitting, where high-cost and low-abundance Pt-based materials are the benchmark catalysts for HER. Herein, we report the fabrication of MoP nanoparticles confined in P-doped porous carbon (MoP@PC) via a metal-organic framework-assisted route for the first time. Remarkably, due to the synergistic effects of MoP nanocrystals, P dopant, and porous carbon, the resulting MoP@PC composite exhibits superior HER catalytic activity with an onset overpotential of 97 mV, a Tafel slope of 59.3 mV dec, and good long-term durability, which compares to those of most reported MoP-based HER catalysts. Most importantly, the work opens a new route in the development of high-performance nonprecious HER electrocatalysts derived from MOFs.

Molybdenum‐Based Carbon Hybrid Materials to Enhance the Hydrogen Evolution Reaction

“…Li et al [124] fabricated ah ybrid nanocomposite, an N-P co-doped carbon/RGO-wrapped MoP (MoP@NPG/rGO) hybrid,v ia carburizationa nd phosphidation using Mo-based MOFs prepared from imidazole and MoO 3 precursors.T he MoP@NPC/RGO catalyst showedr emarkableH ER performance and cycling stabilityb ecause of the synergetic contributions of MoP,N PC and rGO. [123] Due to the synergistic effects of MoP nanoparticles, the MoP@PC nanocomposite showedr emarkable catalytic activityt oward HER, as well as robustdurability. [123] Due to the synergistic effects of MoP nanoparticles, the MoP@PC nanocomposite showedr emarkable catalytic activityt oward HER, as well as robustdurability.…”

“…The MoP@NPC/RGO catalyst showed remarkable HER performance and cycling stability because of the synergetic contributions of MoP, NPC and rGO. Furthermore, these workers fabricated another nano‐hybrid of MoP nanoparticles embedded in P‐doped porous carbon (MoP@PC) through a polyoxometalate (POM)‐based MOF‐assisted route followed by carburization and phosphidation (Figure ) . Due to the synergistic effects of MoP nanoparticles, the MoP@PC nanocomposite showed remarkable catalytic activity toward HER, as well as robust durability.…”

“… Schematic of the synthetic protocol for MoP@PC. Reproduced with permission from reference , Copyright 2018, American Chemical Society.…”

“…Reproduced with permission from reference[123],C opyright 2018, American Chemical Society. Reproduced with permission from reference[123],C opyright 2018, American Chemical Society.…”

Two-dimensional metal–organic frameworks and their derivatives for electrochemical energy storage and electrocatalysis

“…[4][5][6] Metal-organic frameworks (MOFs), a series of crystalline materials consisting of metal ions and organic ligands, 7,8 have been extensively investigated for electrochemical energy storage [9][10][11] and electrocatalysis [12][13][14][15] due to their abundant active sites, tunable pore distribution, and controllable morphologies 7,[16][17][18][19][20][21][22][23] Beneting from the ordered arrangement of the metal ions and organic linkers in the MOFs, the MOF derivatives tend to show a homogeneous distribution of the metal atoms or/and metal nanoparticles, 24,25 which could enhance the metal utilization efficiency 26 and further leads to a great improvement for their applications in energy storage and electrocatalysis. To date, carbon materials, 27 metals, 28 transition metal oxides, 25,29,30 transition metal carbides, 31 transition metal dichalcogenides, 32,33 transition metal phosphides, [34][35][36] and their composites 37 have been successfully fabricated from MOF precursors. It is well-known that the morphology of the electrode materials shows a correlation with the ion transport distance, which is a key factor that determines the ion transport resistance and then affects the ion diffusion ability.…”