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Exploring an effective oxygen reduction reaction catalyst via 4e process based on waved-graphene

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  • ReceivedMay 19, 2017
  • AcceptedJun 28, 2017
  • PublishedAug 4, 2017

Abstract

A novel pure and N-doped waved-graphene electro-catalyst with various wavelengths for oxygen reduction reaction (ORR) is explored in acid medium based on the first-principles calculations. The associative and dissociative mechanism are both explored from the O2 adsorption to the H2O formation step by step, from which the dissociative mechanism is likely the only way with an effective 4e process. Furthermore, a very favorable and effective mechanism is proposed for the ORR process, which may provide a guideline on the design of new non-metal electro-catalysts.


Funded by

Science and Technology Development Fund from Macau SAR(FDCT-068/2014/A2)

Multi-Year Research Grant(MYRG2014-00159-FST)

National Natural Science Foundation of China(21671096)

Natural Science Foundation of Shenzhen(JCYJ20150331101823677)


Acknowledgment

This work was supported by the Science and Technology Development Fund from Macau SAR (FDCT-068/2014/A2, FDCT-132/2014/A3, and FDCT-110/2014/SB) and the Multi-Year Research Grant (MYRG2014-00159-FST and MYRG2015-00017-FST) from the Research & Development Office at the University of Macau. The DFT calculations were performed at High Performance Computing Cluster (HPCC) of Information and Communication Technology Office (ICTO) at the University of Macau. It was also supported by Shenzhen Key Laboratory Project (ZDSYS201603311013489), the National Natural Science Foundation of China (21671096), and the Natural Science Foundation of Shenzhen (JCYJ20150331101823677).


Interest statement

The authors declare that they have no conflict of interest.


Contributions statement

Cao L, Yang M, Lu Z and Pan H designed and conceived the research; Cao L wrote the paper with support from Lu Z and Pan H. All authors contributed to the general discussion.


Author information

Lujie Cao is currently a joint PhD student of the University of Macau and Southern University of Science and Technology. He received his MSc degree from Liaocheng University in 2010. He has published more than 10 peer-review papers. His research mainly focuses on the preparation of metal organic frameworks materials and nano-catalyst materials which are applied in energy storage field.

Hui Pan is currently an assistant professor, at the Institute of Applied Physics and Materials Engineering, University of Macau. He received his PhD degree from National University of Singapore in 2006. He is the editorial board member of Advances in Energy Research and Scientific World Journal (Nanotechnology) from 2012. He is also the regular reviewer for more than 40 international SCI journals. His research mainly focuses on energy harvesting and storage, spintronics, nanodevices, magnetism, fabrication and first-principles design of materials and condensed matter physics. He has published more than 100 journal papers (http://www.researcherid.com/rid/A-2702-2009).

Zhouguang Lu is currently an associate professor at the Department of Materials Science and Engineering, Southern University of Science and Technology, China. He received his PhD degree from the City University of Hong Kong in 2009. He is the recipient of Fulbright Fellowship of USA Government in 2008–2009 and the Overseas High-Caliber Personnel (Level B) of Shenzhen government in 2013. His research mainly covers the design and synthesis of nanostructures and their applications in energy storage and conversion with focus on lithium/sodium -ion and -air batteries. He has authored more than 100 peer-review papers with total citations more than 2800 and H-index of 30.

Supplement

Specific structure details are available in the online version of the paper.


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  • Figure 1

    The proposed WG for ORR catalysts. For clarity, C atoms of the WG are displayed in two different colours.

  • Figure 2

    The ORR process based on the dissociative mechanism D1 or D2 and the proposed mechanism in red dashed arrows.

  • Figure 3

    Typical ORR process from O2 adsorption to two H2O molecule desorption from the catalyst p-50 and N-50-doped WG. Upper panel and lower panel are pure and N-doped WG structures with the lowest energy, respectively.

  • Figure 4

    Free energy diagrams (at different electrode potentials) for the ORR on p-50 and N-50-doped WG electrocatalyst in an acidic medium. Dissociative mechanism D1 or D2 (left panel, red line is for p-50 WG at 0.5 V potential) and the proposed mechanism (right panel). The labels are: initial = O2 + *+ 4H+ + e, a = O2*+ 4H+ + e, c = O–HO*+ 3H+ + e, e = HO–HO*+ 2H+ + e, f = HO*+ H2O + H+ + e, g = 2H2O + *, respectively.

  • Table 1   The adsorption energy Ead (eV) of O2 molecule (in singlet (s) and triplet (t)) and OHO intermediate on WG. The O–O distance (Å) of the adsorbed O2 molecule and the corresponding separated O–O. The charge transfer C (e) from the WG to O2 molecule.

    Ead-O2-s

    Ead-O2-t

    Ead-OHO

    DO2

    DO–O

    C

    p-50

    −0.62

    0.47

    −3.87

    1.518

    2.825

    1.01

    p-40

    −0.36

    0.77

    −3.36

    1.516

    2.774

    0.95

    p-30

    −0.09

    1.01

    −2.81

    1.515

    2.727

    0.93

    N-50

    −1.22

    −0.14

    −5.88

    1.517

    2.655

    0.94

    N-40

    −1.05

    0.03

    −5.42

    1.514

    2.609

    0.92

    N-30

    −0.83

    0.25

    −4.88

    1.509

    2.567

    0.90

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