Core-shell hierarchical tungsten carbide composite microspheres towards methanol electrooxidation

ZHONG Sheng-wen; HU Xian-chao; YU Yuan; YU Chang-lin; ZHOU Yang

Volume 46 Issue 5

May 2018

Turn off MathJax

Article Contents

Article Navigation > Journal of Fuel Chemistry and Technology > 2018 > 46(5): 585-591

ZHONG Sheng-wen, HU Xian-chao, YU Yuan, YU Chang-lin, ZHOU Yang. Core-shell hierarchical tungsten carbide composite microspheres towards methanol electrooxidation[J]. Journal of Fuel Chemistry and Technology, 2018, 46(5): 585-591.

Citation:

ZHONG Sheng-wen, HU Xian-chao, YU Yuan, YU Chang-lin, ZHOU Yang. Core-shell hierarchical tungsten carbide composite microspheres towards methanol electrooxidation[J]. Journal of Fuel Chemistry and Technology, 2018, 46(5): 585-591.

Citation:

PDF( 4997 KB)

Core-shell hierarchical tungsten carbide composite microspheres towards methanol electrooxidation

1.
Engineering Research Institute, Jiangxi University of Science and Technology, Ganzhou 341000, China
2.
Key Laboratory of Power Batteries & Relative Materials, Ganzhou 341000, China
3.
Research Center of Analysis and Measurement, Zhejiang University of Technology, Hangzhou 310032, China

Funds:

National Natural Science Foundation of China 51404110

National Natural Science Foundation of China 21567008

National Natural Science Foundation of China 21506187

Education Department Project Fund of Jiangxi Province GJJ150665

Program of 5511 Talents in Scientific and Technological Innovation of Jiangxi Province 20165BCB18014

Undergraduate Innovation Training Program XZG-16-08-14

More Information

Corresponding author: ZHOU Yang, Tel: +86 797 8312341, E-mail: yangzhou1998@126.com
Received Date: 2017-10-13
Rev Recd Date: 2018-03-16

Available Online: 2021-01-23

Publish Date: 2018-05-10

Abstract

Abstract

Tungsten carbides microspheresare synthesized by in situ reduction of ammonium met tungstate microspheres (AMT) precursors as a function of reaction time under CO/CO₂ mixture atmosphere. The morphology, size and composition of the as-prepared tungsten carbide microspheres are characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). Pt nanoparticles with a diameter of 4.6 nm are loaded onto the surface of WC microspheres using a conventional sodium borohydride reduction method. The electro-catalytic activity and stability toward methanol electrooxidation (MOR) are investigated using cyclic voltammetry (CV) and chronoamperometry(CA). The resultant Pt/WCO-6 h catalyst exhibits low onset potential and excellent catalytic performances in comparison to the commercial JM Pt/C and Pt/WC-15 h catalysts. Further investigation shows that besides the synergistic effect between WC and Pt, the existence of WO₂ might also play an important role in improving the electro-catalytic activity, indicating the positive effect of the surface oxide on the activity and stability of Pt/WC catalysts towards MOR.
- direct methanol fuel cells,
- methanol electrooxidation,
- tungsten carbide,
- electro-catalyst,
- tungsten oxidation

FullText(HTML)

References(35)

References

[1]	LANG X, SHI M, JIANG Y, CHEN H, MA C. Tungsten carbide/porous carbon core-shell nanocomposites as a catalyst support for methanol oxidation[J]. RSC Adv, 2016, 6(17):13873-13880 doi: 10.1039/C5RA18817B
[2]	JING S C, GUO X L, TAN Y W. Branched Pd and Pd-based trimetallic nanocrystals with highly open structures for methanol electrooxidation[J]. J Mater Chem A, 2016, 4(20):7950-7961. doi: 10.1039/C5TA10046A
[3]	ZHOU Y, HU X C, ZENG M, FU J X, ZHONG S W. Platinum nanoparticles supported on three-dimensionalgraphene as electro-cacatalyst for methanol oxidation[J]. J Fuel Chem Technol, 2017, 45(2):194-199.
[4]	CHEN Z Y, MA C A, ChU Y Q, JIN J M, LIN X, HARDACRE C, LIN W F. WC@meso-Pt core-shell nanostructures for fuel cells[J]. Chem Commun, 2013, 49(99):11677-11679. doi: 10.1039/c3cc46595k
[5]	MA C A, LIU W, SHI M, LANG X, CHU Y, CHEN Z, ZHAO D, LIN W, HARDACRE C. Low loading platinum nanoparticles on reduced graphene oxide-supported tungsten carbide crystallites as a highly active electrocatalyst for methanol oxidation[J]. Electrochim Acta, 2013, 114:133-141. doi: 10.1016/j.electacta.2013.10.034
[6]	GANESAN R, HAM D J, LEE J S. Platinized mesoporous tungsten carbide for electrochemical methanol oxidation[J]. Electrochem Commun, 2007, 9(10):2576-2579. doi: 10.1016/j.elecom.2007.08.002
[7]	MELLINGER Z J, KELLY T G, CHEN J G. Pd-Modified tungsten carbide for methanol electro-oxidation:From surface science studies to electrochemical evaluation[J]. ACS Catal, 2012, 2(5):751-758. doi: 10.1021/cs200620x
[8]	ZELLNER M B, CHEN J G. Surface science and electrochemical studies of WC and W₂C PVD films as potential electrocatalysts[J]. Catal Today, 2005, 99(3/4):299-307.
[9]	WEIGERT E C, ZELLNER M B, STOTTLEMYER A L, CHEN J G. A combined surface science and electrochemical study of tungsten carbides as anode electrocatalysts[J]. Top Catal, 2007, 46(3/4):349-357 doi: 10.1007/s11244-007-9006-7.pdf
[10]	WANG Y, SONG S, MARAGOU V, SHEN P K. TSIAKARAS P. High surface area tungsten carbide microspheres as effective Pt catalyst support for oxygen reduction reaction[J]. Appl Catal B:Environ, 2009, 89:223-228. doi: 10.1016/j.apcatb.2008.11.032
[11]	GANESAN R, LEE J S. Tungsten carbide microspheres as a noble-metal-economic electrocatalyst for methanol oxidation[J]. Angew Chem, Int Ed, 2005, 44:6557-6560. doi: 10.1002/(ISSN)1521-3773
[12]	HAM D J, GANESAN R, LEE J S. Tungsten carbide microsphere as an electrode for cathodic hydrogen evolution from water[J]. Int J Hydrogen Energy, 2008, 33:6865-6872. doi: 10.1016/j.ijhydene.2008.05.045
[13]	HUNT S T, NIMMANWUDIPONG T, ROMAN-LESHKOV Y. Engineering non-sintered, metal-terminated tungsten carbide nanoparticles for catalysis[J]. Angew Chem, Int Ed, 2014, 126(20):5231-5236 doi: 10.1002/ange.v126.20
[14]	XIAO P, GE X, WANG H, LIU Z, FISHER A, WANG X. Novel molybdenum carbide-tungsten carbide composite nanowires and their electrochemical activation for efficient and stable hydrogen evolution[J]. Adv Funct Mater, 2015, 25(10):1520-1526 doi: 10.1002/adfm.201403633
[15]	YANG X, KIMMEL Y C, FU J, KOEL B E, CHEN J G. Activation of tungsten carbide catalysts by use of an oxygen plasma pretreatment[J]. ACS Catal, 2012, 2(5):765-769. doi: 10.1021/cs300081t
[16]	KIMMEL Y C, ESPOSITO D V, BIRKMIRE R W, CHEN J G. Effect of surface carbon on the hydrogen evolution reactivity of tungsten carbide (WC) and Pt-modified WC electrocatalysts[J]. Int J Hydrogen Energy, 2012, 37(4):3019-3024. doi: 10.1016/j.ijhydene.2011.11.079
[17]	HUNT S T, MILINA M, ALBA-RUBIO A C, HENDON C H, DUMESIC J A, ROMAN-LESHKOV Y. Self-assembly of noble metal monolayers on transition metal carbide nanoparticle catalysts[J]. Science, 2016, 352(6288):974-978. doi: 10.1126/science.aad8471
[18]	HUNT S T, KOKUMAI T M, ZANCHET D, ROMANLESHKOV Y. Alloying tungsten carbide nanoparticles with tantalum:Impact on electrochemical oxidation resistance and hydrogen evolution activity[J]. J Phys Chem C, 2015, 119(24). http://cn.bing.com/academic/profile?id=b15fb4d9cc782aea653ca3ead0da4452&encoded=0&v=paper_preview&mkt=zh-cn
[19]	HOOR F S, AHMED M F, MAYANNA S M. Methanol oxidative fuel cell:Electrochemical synthesis and characterization of low-priced WO₃-Pt anode material[J]. J Solid State Electrochem, 2004, 8(8):572-576. https://www.researchgate.net/publication/244033746_Methanol_oxidative_fuel_cell_Electrochemical_synthesis_and_characterization_of_low-priced_WO3-Pt_anode_material
[20]	YE J L, LIU J G, ZOU ZG, GU J, YU T. Preparation of Pt supported on WO₃-C with enhanced catalytic activity by microwave-pyrolysis method[J]. J Power Sources, 2010, 195(9):2633-2637. doi: 10.1016/j.jpowsour.2009.11.055
[21]	ZHOU Y, HU X C, LIU XH, WEN H R. Core-shell hierarchical WO₂/WO₃ microspheres as an electrocatalyst support for methanol electrooxidation[J]. Chem Commun, 2015, 51:15297-15299. doi: 10.1039/C5CC06603D
[22]	ZHOU Y, HU X C, XIAO Y J, SHU Q. Platinum nanoparticles supported on hollow mesoporous tungsten trioxide microsphere as electrocatalyst for methanol oxidation[J]. Electrochim Acta, 2013, 111:588-592. doi: 10.1016/j.electacta.2013.08.057
[23]	GANESAN R, LEE J S. Tungsten carbide microspheres as a noble-metal-economic electrocatalyst for methanol oxidation[J]. Angew Chem, Int Ed, 2005, 44(40):6557-6560. doi: 10.1002/(ISSN)1521-3773
[24]	MA C A, BRANDON N, LI G. Preparation and formation mechanism of hollow microspherical tungsten carbide with mesoporosity[J]. J Phys Chem C, 2007, 111(26):9504-9508. doi: 10.1021/jp072378q
[25]	KATRIB A, HEMMING F, WEHRER P, HILAIRE L, MAIRE G. Surface characterization and catalytic properties of supported tungsten and platinum-tungsten carbide and oxycarbide[J]. Top Catal, 1994, 1(1/2):75-85. doi: 10.1007/BF01379577.pdf
[26]	LANG X, SHI M, CHU Y, LIU W, CHEN Z, MA C. Microwave-assisted synthesis of Pt-WC/TiO₂ in ionic liquid and its application for methanol oxidation[J]. J Solid State Electrochem, 2013, 17(9):2401-2408. doi: 10.1007/s10008-013-2060-0
[28]	LIM B, JIANG M, CAMARGO P H C, CHO E C, TAO J, LU X, ZHU Y, XIA Y. Pd-Pt bimetallic nanodendrites with high activity for oxygen reduction[J]. Science, 2009, 324(5932):1302. doi: 10.1126/science.1170377
[28]	CHEN S, WEI Z, QI X Q, DONG L, GUO Y G, WAN L, SHAO Z, LI L. Nanostructured polyaniline-decorated Pt/C@PANI core-shell catalyst with enhanced durability and activity[J]. J Am Chem Soc, 2012, 134(32):13252. doi: 10.1021/ja306501x
[29]	GUO S, DONG S, WANG E. Constructing carbon nanotube/Pt nanoparticle hybrids using an imidazolium-salt-based ionic liquid as a linker[J]. Adv Mater, 2010, 22(11):1269-1272. doi: 10.1002/adma.v22:11
[30]	CHANG J, FENG L, LIU C, XING W, HU X. Ni₂P enhances the activity and durability of the Pt anode catalyst in direct methanol fuel cells[J]. Energy Environ Sci, 2014, 7(5):1628-1632. doi: 10.1039/c4ee00100a
[31]	MELLINGER Z J, KELLY T G, CHEN J G G. Pd-Modified tungsten carbide for methanol electro-oxidation:From surface science studies to electrochemical evaluation[J]. ACS Catal, 2012, 2(5):751-758. doi: 10.1021/cs200620x
[32]	KELLY T G, STOTTLEMYER A L, REN H, CHEN J G. Comparison of O-H, C-H, and C-O bond scission sequence of methanol on tungsten carbide surfaces modified by Ni, Rh, and Au[J]. J Phys Chem C, 2011, 115(14):6644-6650. doi: 10.1021/jp112006v
[33]	AND H H H, CHEN J G, AND K K, LAVIN J G. Potential application of tungsten carbides as electrocatalysts. 1. Decomposition of methanol over carbide-modified W(111)[J]. J Phys Chem B, 2001, 105(41):10037-10044. doi: 10.1021/jp0116196
[34]	TSEUNG A C C, CHEN K Y. Hydrogen spill-over effect on Pt/WO₃ anode catalysts[J]. Catal Today, 1997, 38(4):439-443. doi: 10.1016/S0920-5861(97)00053-9
[35]	SHEN P K, CHEN K Y, TSEUNG A C C. Performance of Co-electrodeposited Pt-Ru/WO₃ electrodes for the electrooxidation of formic-acid at room-temperature[J]. J Electroanal Chem, 1995, 389(1/2):223-225. https://www.sciencedirect.com/science/article/pii/002207289503974L