气候变化领域集成服务门户(CCPortal): Phosphorus-Mo2C@carbon nanowires toward efficient electrochemical hydrogen evolution: Composition, structural and electronic regulation

CCPortal

DOI	10.1039/c7ee00388a
	Phosphorus-Mo2C@carbon nanowires toward efficient electrochemical hydrogen evolution: Composition, structural and electronic regulation
	Shi Z.; Nie K.; Shao Z.-J.; Gao B.; Lin H.; Zhang H.; Liu B.; Wang Y.; Zhang Y.; Sun X.; Cao X.-M.; Hu P.; Gao Q.; Tang Y.
发表日期	2017
ISSN	17545692
起始页码	1262
结束页码	1271
卷号	10 期号:5
英文摘要	To explore high-performance electrocatalysts, electronic regulation on active sites is essentially demanded. Herein, we propose controlled phosphorus doping to effectively modify the electronic configuration of nanostructured Mo2C, accomplishing a benchmark performance of noble-metal-free electrocatalysts in the 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 integrated 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 the Fermi level of Mo2C, leading to weakened Mo-H bonding toward promoted HER kinetics. Further density functional 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 the Mo2C surface, indicating the effectively weakened strength of Mo-H. With optimal doping, a ΔGH∗ approaching 0 eV suggests a good balance between the Volmer and Heyrovsky/Tafel steps in HER kinetics. As expected, the P-Mo2C@C nanowires with controlled P-doping (P: 2.9 wt%) deliver a low overpotential of 89 mV at a 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 the current noble-metal-free electrocatalysts. Elucidating feasible electronic regulation and the remarkably enhanced catalysis associated with controlled P-doping, our work will pave the way for developing efficient noble-metal-free catalysts via rational surface engineering. © 2017 The Royal Society of Chemistry.
英文关键词	Benchmarking; Binding energy; Carbon; Chemical bonds; Electrocatalysts; Electrolysis; Free energy; Kinetics; Molybdenum oxide; Nanowires; Phosphorus; Polyaniline; Precious metals; Acidic electrolytes; Electronic configuration; Hydrogen evolution; Hydrogen evolution reactions; Metal-free catalysts; Metal-free electrocatalysts; Steric hindrances; Surface engineering; Density functional theory; benchmarking; carbon nanotube; catalysis; electrochemistry; electron density; hydrogen; organic acid; performance assessment; phosphorus; pyrolysis; reaction kinetics
语种	英语
来源期刊	Energy & Environmental Science
文献类型	期刊论文
条目标识符	http://gcip.llas.ac.cn/handle/2XKMVOVA/190546
作者单位	Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Laboratory of Advanced Materials, Collaborative Innovation Center of Chemistry for Energy Materials, Department of Chemistry, Fudan University, Shanghai, 200433, China; Department of Chemistry, Jinan University, Guangzhou, 510632, China; Key Laboratory for Advanced Materials, Center for Computational Chemistry, Research Institute of Industrial Catalysis, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai, 200237, China; Institute of Functional Nano and Soft Materials (FUNSOM), Jiangsu Key Laboratory for Carbon-Based Functional Materials and Devices, Soochow University, Suzhou, 215123, China
推荐引用方式 GB/T 7714	Shi Z.,Nie K.,Shao Z.-J.,et al. Phosphorus-Mo2C@carbon nanowires toward efficient electrochemical hydrogen evolution: Composition, structural and electronic regulation[J],2017,10(5).
APA	Shi Z..,Nie K..,Shao Z.-J..,Gao B..,Lin H..,...&Tang Y..(2017).Phosphorus-Mo2C@carbon nanowires toward efficient electrochemical hydrogen evolution: Composition, structural and electronic regulation.Energy & Environmental Science,10(5).
MLA	Shi Z.,et al."Phosphorus-Mo2C@carbon nanowires toward efficient electrochemical hydrogen evolution: Composition, structural and electronic regulation".Energy & Environmental Science 10.5(2017).