文献类型：期刊文献

英文题名：Phosphorus-Mo2C@carbon nanowires toward efficient electrochemical hydrogen evolution: composition, structural and electronic regulation

作者：Shi, Zhangping[1,2];Nie, Kaiqi[6,7];Shao, Zheng-Jiang[4,5];Gao, Boxu[1,2];Lin, Huanlei[3];Zhang, Hongbin[1,2];Liu, Bolun[1,2];Wang, Yangxia[1,2];Zhang, Yahong[1,2];Sun, Xuhui[6,7];Cao, Xiao-Ming[4,5];Hu, P.[4,5];Gao, Qingsheng[3];Tang, Yi[1,2]

机构：[1]Fudan Univ, Lab Adv Mat, Shanghai Key Lab Mol Catalysis & Innovat Mat, Shanghai 200433, Peoples R China;[2]Fudan Univ, Dept Chem, Collaborat Innovat Ctr Chem Energy Mat, Shanghai 200433, Peoples R China;[3]Jinan Univ, Dept Chem, Guangzhou 510632, Guangdong, Peoples R China;[4]East China Univ Sci & Technol, Ctr Computat Chem, Key Lab Adv Mat, Shanghai 200237, Peoples R China;[5]East China Univ Sci & Technol, Res Inst Ind Catalysis, Sch Chem & Mol Engn, Shanghai 200237, Peoples R China;[6]Soochow Univ, Inst Funct Nano & Soft Mat FUNSOM, Suzhou 215123, Peoples R China;[7]Soochow Univ, Jiangsu Key Lab Carbon Based Funct Mat & Devices, Suzhou 215123, Peoples R China

年份：2017

卷号：10

期号：5

起止页码：1262

外文期刊名：ENERGY & ENVIRONMENTAL SCIENCE

收录：;EI(收录号：20173003970836);WOS:【SCI-EXPANDED(收录号:WOS:000401408500021)】；

基金：The authors appreciate the financial support of the National Key Basic Research Program of China (2013CB934101), NSFC (21433002, 21373102, 21573046, 21673072, 21333003), Q. S. Gao is also grateful for support from the Natural Science Foundation of Guangdong Province (2015A030306014 and 2014TQ01N036). K. Q. Nie and X. H. Sun thank the financial support from the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD) and Collaborative Innovation Center of Suzhou Nano Science & Technology. The authors thank NSRRC beamline scientist Dr Ting-Shan Chan for the technical support, and also Chung-Li Dong and Xiaosong Liu for the great help with the X-ray measurements. The authors also express their gratitude to Dr Qiangsheng Guo from Shanghai Institute of Technology for XPS and UPS measurements and analysis.

语种：英文

外文关键词：Chemical bonds - Precious metals - Benchmarking - Carbon - Free energy - Kinetics - Density functional theory - Polyaniline - Phosphorus - Binding energy

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 (Delta G(H)*) 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 Delta G(H)* 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.