Preparation and Electrocatalytic Activity of Nitrogen-Doping Tungsten Carbide Catalyst

Authors

Pian-pian YANG, State Key Laboratory Breeding Base of Green Chemistry-Synthesis Technology, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310032, Zhejiang, China;
Li-zhen HUANG, State Key Laboratory Breeding Base of Green Chemistry-Synthesis Technology, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310032, Zhejiang, China;
Ying-ying LI, State Key Laboratory Breeding Base of Green Chemistry-Synthesis Technology, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310032, Zhejiang, China;
Mei-qin SHI, State Key Laboratory Breeding Base of Green Chemistry-Synthesis Technology, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310032, Zhejiang, China;Follow
Chun-an MA, State Key Laboratory Breeding Base of Green Chemistry-Synthesis Technology, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310032, Zhejiang, China;

Corresponding Author

Mei-qin SHI(smq@zjut.edu.cn)

Abstract

Tungsten carbide (WC) is a promising electrocatalyst, however, its electrocatalytic activity is far inferior to Pt and Pt-group metal. In this work, nitrogen-doping tungsten carbide (WN|WC) catalysts with a nanoplate morphology were prepared via the tungsten nitride (WN) as the precursor and sodium tungstate as the tungsten source. The SEM and TEM results indicated that carbon atoms entered into the WN lattice to form the hexagonal close packed WC phase. In this way, an atomic scale heterostructure involving the closely linked interfaces between WN and WC was created . The XRD data confirmed that the cubic crystal structure of WN was still reserved after carbonization. The XPS analyses also verified the existences of W-N and W-C. In order to discuss the effect of nitrogen doping on the catalytic performance of WN|WC, Pt/WN|WC catalyst was prepared by ethylene glycol reduction with microwave-assisted heating method. The electrochemical properties of Pt/WN|WC catalyst in methanol oxidation reaction were evaluated and compared with those of pure WC and commercial Pt/C catalysts. Electrochemical tests demonstrated that the peak current density of Pt/WN|WC was three times as that of commercial Pt/C. In addition, the excellent exchange current density, rate constant and the stable Ep_f and Ep_b values suggested that the nanoplate Pt/WN|WC has a promising application as an anode material for direct methanol fuel cells.

Graphical Abstract

Keywords

tungsten carbide, trogen-doping, heterostructure, change current density, rate constant

DOI Link

https://doi.org/10.13208/j.electrochem.170222

Publication Date

2018-02-28

Online Available Date

2017-03-30

Revised Date

2017-03-28

Received Date

2017-02-22

Recommended Citation

Pian-pian YANG, Li-zhen HUANG, Ying-ying LI, Mei-qin SHI, Chun-an MA. Preparation and Electrocatalytic Activity of Nitrogen-Doping Tungsten Carbide Catalyst[J]. Journal of Electrochemistry, 2018 , 24(1): 63-71.
DOI: 10.13208/j.electrochem.170222
Available at: https://jelectrochem.xmu.edu.cn/journal/vol24/iss1/8

References

[1] Sun S G(孙世刚)，Chen S L(陈胜利). Electrocatalysis[M]. Beijing: Chemical Industry Press(化学工业出版社), 2013: 11-20.
[2] Levy R B, Boundart M. Platinum-like behavior of tungsten carbide in surface catalysis[J]. Science, 1973, 181(4099): 547-549.
[3] Poh C K, Lim S H, Lin J, et al. Tungsten carbide supports for single-atom platinum-based fuel-cell catalysts: First-principles study on the metal-support interactions and O₂ dissociation on WxC low-index surfaces[J]. Journal of Physical Chemistry C, 2014, 118(25): 13525-13538.
[4] Shi J, Pu Z H, Liu Q, et al. Tungsten nitride nanorods array grown on carbon cloth as an efficient hydrogen evolution cathode at all pH values[J]. Electrochimica Acta, 2015, 154(24): 345-351.
[5] Dong Y, Li J H. Tungsten nitride nanocrystals on nitrogen-doping carbon black as efficient electrocatalysts for oxygen reduction reactions[J]. Chemical Communications, 2015, 51(3): 572-575.
[6] Yin S B, Yang L X, Luo L, et al. Fabrication and performance investigation of nanocrystal tungsten nitride supported Pt catalysts for methanol electrooxidation[J]. New Journal of Chemistry, 2013, 37(37): 3976-3980.
[7] Zhao Y, Kamiya K, Hashimoto K, et al. In situ CO₂-emission assisted synthesis of molybdenum carbonitride nanomaterial as hydrogen evolution electrocatalyst[J]. Journal of the American Chemical Society, 2015, 137(1): 110-113.
[8] Zhao Y, Kamiya K, Hashimoto K, et al. Hydrogen evolution by tungsten carbonitride nanoelectrocatalysts synthesized by the formation of a tungsten acid/polymer hybrid in situ[J]. Angewandte Chemie International Edition, 2013, 125(51): 13638 -13641.
[9] Sun S K，Kan Y M，Ni D W, et al. Synthesis mechanism and sintering behavior of tungsten carbide powder produced by a novel solid state reaction of W₂N[J]. Industrial Journal of Refractory Metals and Hard Materials, 2012, 35(1): 202-206.
[10] Hara Y，Minami N，Itagaki H. Synthesis and characterization of high-surface area tungsten carbides and application to electrocatalytic hydrogen oxidation[J]. Applied Catalysis A: General, 2007, 323(5): 86-93.
[11] Hara Y，Minami N，Matsumoto H, et al. New synthesis of tungsten carbide particles and the synergistic effect with Pt metal as a hydrogen oxidation catalyst for fuel cell applications[J]. Applied Catalysis A: General, 2007, 332(2): 289-296.
[12] Ospina R, Escobar D, Restrepo-Parra E, et. al. Mechanical and tribological behavior of W/WCN bilayers grown by pulsed vacuum arc discharge[J]. Tribology International, 2013, 62(6): 124-129..
[13] Fernandes D M, Brett C M A, Cavaleiro A M V. Layer-by-layer self-assembly and electrocatalytic properties of poly (ethylenimine)-silicotungstate multilayer composite films[J]. Journal of Solid State Electrochem, 2011, 15(4): 811-819.
[14] Estrade-Szwarckopf H. XPS photoemission in carbonaceous materials: A €œdefect€peak beside the graphitic asymmetric peak[J]. Carbon, 2004, 42(8): 1713-1721.
[15] Ababou-Girard S, Sabbah H, Fabre B, et al. Covalent82(2): 150-153.
[20] Zellner M B, Chen J G. Surface science and electrochemical studies of WC and W₂C PVD films as potential electrocatalysts[J]. Catalyst Today, 2005, 99(3/4): 299-307.
[21] Yaldagard M, Jahanshahi M, Seghatoleslami N. Pt catalysts on PANI coated WC/C nanocomposites for methanol electro-oxidation and oxygen electro-reduction in DMFC[J]. Applied Surface Science, 2014, 317: 496-504.
[22] Ma C A, Liu W M, Shi M Q, et al. Low loading platinum nanoparticles on reduced grapheme oxide-supported tungsten carbide crystallites as a highly active electrocatalyst for methanol oxidation[J]. Electrochimica Acta, 2013, 114(114): 133-141.
[23] Khan A S A, Riaz A, Latif M M. Evaluation of catalytic activity of Pt and Pt-Ru catalysts for electro-oxidation of methanol in acid medium by cyclic voltammetry[J]. Electrochimca Acta, 2009, 27(4): 429-441.
[24] Lin W F(林文锋), Sun S G(孙世刚), Tian Z Q(田中群), et al. 电化学界面吸附的微观横形和量子化学处理[J].Chinese Science Bulletin(科学通报), 1993, 38(24): 2252-2254.
[25] Sugimoto W, Aoyama K, Kawaguchi T, et al. Kinetics of CH₃OH oxidation on PtRu/C studied by impedance and CO stripping voltammetry[J]. Journal of Electroanalytical Chemistry, 2005, 576(2): 215-221.
[26] Hwu H H, Chen J G. Surface chemistry of transition metal carbides[J]. Chemical Reviews, 2004, 105(1): 185-212.
[27] Stottlemyer A L, Weigert E C, Chen J G. Tungsten carbides as alternative electrocatalysts: From surface science studies to fuel cell evaluation[J]. Industrial & Engineering Chemistry Research, 2010, 50(1): 16-22.
[28] Jeon M K, Hideo Daimon, et al. CO tolerant Pt/WC methanol electro-oxidation catalyst[J]. Electrochemistry Communications, 2007, 9(11): 2692-2695.
[29] Fu Z, Huang Q M, Xiang X D, et al. Mesoporous tungsten carbide-supported platinum as carbon monoxide-tolerant electrocatalyst for methanol oxidation[J]. Fuel & Energy Abstracts, 2012, 37(5): 4704-4709.
[30] Ren H, Danielle A H, Alan L, et al. Replacing platinum with tungsten carbide (WC) for reforming reactions: Similarities in ethanol decomposition on Ni/Pt and Ni/WC surfaces stottlemyer[J]. ACS Catalysis, 2011, 1(4): 390-398.
[31] Yan H J, Tian C G, Wang L, et al. Phosphorus-modified tungsten nitride/reduced graphene oxide as a high-performance, non-noble-metal electrocatalyst for the hydrogen evolution reaction[J]. Angewandte Chemie International Edition, 2015, 54(21): 6325-6329.