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Phosphorus-Mo2C@Carbon Nanowires toward Efficient Electrochemical Hydrogen Evolution: Composition, Structural and Electronic Regulation


To explore high-performance electrocatalysts, electronic regulation on active sites is essentially demanded. Herein, we propose a controlled phosphorus doping to effective modify the electronic configuration of nanostructured Mo2C, accomplishing the benchmarking performance of noble-metal-free electrocatalysts in hydrogen evolution reaction (HER). Employing MoOx-phytic acid-polyaniline hybrids with tunable composition as precursors, a series of hierarchical nanowires composed of phosphorus-doped Mo2C nanoparticles evenly integrating within conducting carbon (denoted as P-Mo2C@C) are successfully obtained via facile pyrolysis under inert flow. Remarkably, P-doping into Mo2C can increase the electron density around Fermi level of Mo2C, leading to weakened Mo-H bonding toward promoted HER kinetics. The further density function theory calculations show that the negative hydrogen-binding free energy (ΔGH*) on pristine Mo2C gradually increases with P-doping due to electron transfer and steric hindrance by P on Mo2C surface, indicating the effectively weakened strength of Mo-H. With an optimal doping, a ΔGH* approaching to 0 eV suggests a good balance between Volmer and Heyrovsky/Tafel steps in HER kinetics. As expected, the P-Mo2C@C nanowires with a controlled P-doping (P: 2.9 wt.%) delivers a low overpotential of 89 mV at the current density of -10 mA cm-2 and striking kinetic metrics (onset overpotential: 35 mV, Tafel slope: 42 mV dec-1) in acidic electrolytes, outperforming most of current noble-metal-free electrocatalysts. Elucidating the feasible electronic regulation and the remarkably enhanced catalysis associated with controlled P-doping, our work would pave a way for developing efficient noble-metal-free catalysts via rational surface engineering.

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Publication details

The article was received on 10 Feb 2017, accepted on 19 Apr 2017 and first published on 19 Apr 2017

Article type: Paper
DOI: 10.1039/C7EE00388A
Citation: Energy Environ. Sci., 2017, Accepted Manuscript
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    Phosphorus-Mo2C@Carbon Nanowires toward Efficient Electrochemical Hydrogen Evolution: Composition, Structural and Electronic Regulation

    S. Zhangping, K. Nie, Z. Shao, B. Gao, H. Lin, H. Zhang, B. Liu, Y. Wang, Y. Zhang, X. Sun, X. Cao, P. Hu, Q. Gao and Y. Tang, Energy Environ. Sci., 2017, Accepted Manuscript , DOI: 10.1039/C7EE00388A

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