
Platinum on nitrogen doped graphene and tungsten carbide supports for ammonia electro-oxidation reaction
Kumar Siddharth, Yian Wang, Jing Wang, Fei Xiao, Gabriel Sikukuu Nambafu, Usman Bin Shahid, Fei Yang, Ernest Pahuyo Delmo, Minhua Shao
Front. Chem. Sci. Eng. ›› 2022, Vol. 16 ›› Issue (6) : 930-938.
Platinum on nitrogen doped graphene and tungsten carbide supports for ammonia electro-oxidation reaction
Ammonia electrooxidation reaction involving multistep electron-proton transfer is a significant reaction for fuel cells, hydrogen production and understanding nitrogen cycle. Platinum has been established as the best electrocatalyst for ammonia oxidation in aqueous alkaline media. In this study, Pt/nitrogen-doped graphene (NDG) and Pt/tungsten monocarbide (WC)/NDG are synthesized by a wet chemistry method and their ammonia oxidation activities are compared to commercial Pt/C. Pt/NDG exhibits a specific activity of 0.472 mA∙cm–2, which is 44% higher than commercial Pt/C, thus establishing NDG as a more effective support than carbon black. Moreover, it is demonstrated that WC as a support also impacts the activity with further 30% increase in comparison to NDG. Surface modification with Ir resulted in the best electrocatalytic activity with Pt-Ir/WC/NDG having almost thrice the current density of commercial Pt/C. This work adds insights regarding the role of NDG and WC as efficient supports along with significant impact of Ir surface modification.
Ammonia electro-oxidation reaction / electrocatalyst supports / platinum / nitrogen doped graphene / tungsten carbide
[1] |
Siddharth K, Chan Y, Wang L, Shao M. Ammonia electro-oxidation reaction: recent development in mechanistic understanding and electrocatalyst design. Current Opinion in Electrochemistry, 2018, 9: 151–157
CrossRef
Google scholar
|
[2] |
Li Z F, Wang Y, Botte G. Revisiting the electrochemical oxidation of ammonia on carbon-supported metal nanoparticle catalysts. Electrochimica Acta, 2017, 228: 351–360
CrossRef
Google scholar
|
[3] |
Boggs B K, Botte G. On-board hydrogen storage and production: an application of ammonia electrolysis. Journal of Power Sources, 2009, 192(2): 573–581
CrossRef
Google scholar
|
[4] |
Zhong C, Hu W B, Cheng Y F. Recent advances in electrocatalysts for electro-oxidation of ammonia. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2013, 1(10): 3216–3238
CrossRef
Google scholar
|
[5] |
Chan Y T, Siddharth K, Shao M. Investigation of cubic Pt alloys for ammonia oxidation reaction. Nano Research, 2020, 13(7): 1920–1927
CrossRef
Google scholar
|
[6] |
Siddharth K, Hong Y, Qin X, Lee H J, Chan Y T, Zhu S, Chen G, Choi S I, Shao M. Surface engineering in improving activity of Pt nanocubes for ammonia electrooxidation reaction. Applied Catalysis B: Environmental, 2020, 269: 118821
CrossRef
Google scholar
|
[7] |
Siddharth K, Alam P, Hossain M D, Xie N, Nambafu G S, Rehman F, Lam J W, Chen G, Cheng J, Luo Z, Chen G, Tang B Z, Shao M. Hydrazine detection during ammonia electro-oxidation using an aggregation-induced emission dye. Journal of the American Chemical Society, 2021, 143(5): 2433–2440
CrossRef
Google scholar
|
[8] |
Vitse F, Cooper M, Botte G. On the use of ammonia electrolysis for hydrogen production. Journal of Power Sources, 2005, 142(1-2): 18–26
CrossRef
Google scholar
|
[9] |
Abbasi R, Setzler B P, Wang J, Zhao Y, Wang T, Gottesfeld S, Yan Y. Low-temperature direct ammonia fuel cells: recent developments and remaining challenges. Current Opinion in Electrochemistry, 2020, 21: 335–344
CrossRef
Google scholar
|
[10] |
Guo Y, Pan Z, An L. Carbon-free sustainable energy technology: direct ammonia fuel cells. Journal of Power Sources, 2020, 476: 228454
CrossRef
Google scholar
|
[11] |
Herron J A, Ferrin P, Mavrikakis M. Electrocatalytic oxidation of ammonia on transition-metal surfaces: a first-principles study. Journal of Physical Chemistry C, 2015, 119(26): 14692–14701
CrossRef
Google scholar
|
[12] |
Boggs B K, Botte G. Optimization of Pt-Ir on carbon fiber paper for the electro-oxidation of ammonia in alkaline media. Electrochimica Acta, 2010, 55(19): 5287–5293
CrossRef
Google scholar
|
[13] |
Bonnin E P, Biddinger E J, Botte G. Effect of catalyst on electrolysis of ammonia effluents. Journal of Power Sources, 2008, 182(1): 284–290
CrossRef
Google scholar
|
[14] |
Cooper M, Botte G. Hydrogen production from the electro-oxidation of ammonia catalyzed by platinum and rhodium on raney nickel substrate. Journal of the Electrochemical Society, 2006, 153(10): A1894
CrossRef
Google scholar
|
[15] |
Daramola D A, Botte G. Theoretical study of ammonia oxidation on platinum clusters—adsorption of ammonia and water fragments. Computational & Theoretical Chemistry, 2012, 989: 7–17
CrossRef
Google scholar
|
[16] |
Rees N V, Compton R G. Carbon-free energy: a review of ammonia- and hydrazine-based electrochemical fuel cells. Energy & Environmental Science, 2011, 4(4): 1255–1260
CrossRef
Google scholar
|
[17] |
Adli N M, Zhang H, Mukherjee S, Wu G. Ammonia oxidation electrocatalysis for hydrogen generation and fuel cells. Journal of the Electrochemical Society, 2018, 165(15): J3130–J3147
CrossRef
Google scholar
|
[18] |
Shanmugam S, Gedanken A. Carbon‐coated anatase TiO2 nanocomposite as a high-performance electrocatalyst support. Small, 2007, 3(7): 1189–1193
CrossRef
Google scholar
|
[19] |
Chai G S, Yoon S B, Kim J H, Yu J S. Spherical carbon capsules with hollow macroporous core and mesoporous shell structures as a highly efficient catalyst support in the direct methanol fuel cell. Chemical Communications, 2004, (23): 2766–2767
CrossRef
Google scholar
|
[20] |
Chandler G K, Genders J D, Pletcher D. Electrodes based on noble metals. Platinum Metals Review, 1997, 41(2): 54–63
|
[21] |
Takasaki F, Matsuie S, Takabatake Y, Noda Z, Hayashi A, Shiratori Y, Ito K, Sasaki K. Carbon-free Pt electrocatalysts supported on SnO2 for polymer electrolyte fuel cells: electrocatalytic activity and durability. Journal of the Electrochemical Society, 2011, 158(10): B1270
CrossRef
Google scholar
|
[22] |
Jayabal S, Saranya G, Geng D, Lin L Y, Meng X. Insight into the correlation of Pt-support interactions with electrocatalytic activity and durability in fuel cells. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2020, 8(19): 9420–9446
CrossRef
Google scholar
|
[23] |
Vidal-Iglesias F J, Solla-Gullón J, Montiel V, Feliu J M, Aldaz A. Screening of electrocatalysts for direct ammonia fuel cell: ammonia oxidation on PtMe (Me: Ir, Rh, Pd, Ru) and preferentially oriented Pt (1 0 0) nanoparticles. Journal of Power Sources, 2007, 171(2): 448–456
CrossRef
Google scholar
|
[24] |
Wang X, Kong Q, Han Y, Tang Y, Wang X, Huang X, Lu T. Construction of Ir-Co/C nanocomposites and their application in ammonia oxidation reaction. Journal of Electroanalytical Chemistry (Lausanne, Switzerland), 2019, 838: 101–106
CrossRef
Google scholar
|
[25] |
Lomocso T L, Baranova E A. Electrochemical oxidation of ammonia on carbon-supported bi-metallic PtM (M= Ir, Pd, SnOx) nanoparticles. Electrochimica Acta, 2011, 56(24): 8551–8558
CrossRef
Google scholar
|
[26] |
Samad S, Loh K S, Wong W Y, Lee T K, Sunarso J, Chong S T, Daud W R. Carbon and non-carbon support materials for platinum-based catalysts in fuel cells. International Journal of Hydrogen Energy, 2018, 43(16): 7823–7854
CrossRef
Google scholar
|
[27] |
Chen M, Liu J, Zhou W, Lin J, Shen Z. Nitrogen-doped graphene-supported transition-metals carbide electrocatalysts for oxygen reduction reaction. Scientific Reports, 2015, 5(1): 1–10
CrossRef
Google scholar
|
[28] |
Fei H, Dong J, Arellano-Jiménez M J, Ye G, Dong Kim N, Samuel E L G, Peng Z, Zhu Z, Qin F, Bao J, Yacaman M J, Ajayan P M, Chen D, Tour J M. Atomic cobalt on nitrogen-doped graphene for hydrogen generation. Nature Communications, 2015, 6(1): 1–8
CrossRef
Google scholar
|
[29] |
Zhang C, Sha J, Fei H, Liu M, Yazdi S, Zhang J, Zhong Q, Zou X, Zhao N, Yu H, Jiang Z, Ringe E, Yakobson B I, Dong J, Chen D, Tour J M. Single-atomic ruthenium catalytic sites on nitrogen-doped graphene for oxygen reduction reaction in acidic medium. ACS Nano, 2017, 11(7): 6930–6941
CrossRef
Google scholar
|
[30] |
Wu G, Li D, Dai C, Wang D, Li N. Well-dispersed high-loading Pt nanoparticles supported by shell-core nanostructured carbon for methanol electrooxidation. Langmuir, 2008, 24(7): 3566–3575
CrossRef
Google scholar
|
[31] |
Lepró X, Terrés E, Vega-Cantú Y, Rodríguez-Macías F J, Muramatsu H, Kim Y A, Hayahsi T, Endo M, Torres M, Terrones M. Efficient anchorage of Pt clusters on N-doped carbon nanotubes and their catalytic activity. Chemical Physics Letters, 2008, 463(1-3): 124–129
CrossRef
Google scholar
|
[32] |
Chhina H, Campbell S, Kesler O. High surface area synthesis, electrochemical activity, and stability of tungsten carbide supported Pt during oxygen reduction in proton exchange membrane fuel cells. Journal of Power Sources, 2008, 179(1): 50–59
CrossRef
Google scholar
|
[33] |
Esposito D V, Chen J G. Monolayer platinum supported on tungsten carbides as low-cost electrocatalysts: opportunities and limitations. Energy & Environmental Science, 2011, 4(10): 3900–3912
CrossRef
Google scholar
|
[34] |
Ganesan R, Lee J S. Tungsten carbide microspheres as a noble-metal-economic electrocatalyst for methanol oxidation. Angewandte Chemie International Edition, 2005, 44(40): 6557–6560
CrossRef
Google scholar
|
[35] |
Meng H, Shen P K. Tungsten carbide nanocrystal promoted Pt/C electrocatalysts for oxygen reduction. Journal of Physical Chemistry B, 2005, 109(48): 22705–22709
CrossRef
Google scholar
|
[36] |
Shao M, Merzougui B, Shoemaker K, Stolar L, Protsailo L, Mellinger Z J, Hsu I J, Chen J G. Tungsten carbide modified high surface area carbon as fuel cell catalyst support. Journal of Power Sources, 2011, 196(18): 7426–7434
CrossRef
Google scholar
|
[37] |
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. Applied Catalysis B: Environmental, 2009, 89(1-2): 223–228
CrossRef
Google scholar
|
[38] |
Zhang J, Chen J, Jiang Y, Zhou F, Wang G, Wang R. Tungsten carbide encapsulated in nitrogen-doped carbon with iron/cobalt carbides electrocatalyst for oxygen reduction reaction. Applied Surface Science, 2016, 389: 157–164
CrossRef
Google scholar
|
[39] |
Hwu H, Chen J G. Surface chemistry of transition metal carbides. Chemical Reviews, 2005, 105(1): 185–212
CrossRef
Google scholar
|
[40] |
Liu Y, Mustain W E. Evaluation of tungsten carbide as the electrocatalyst support for platinum hydrogen evolution/oxidation catalysts. International Journal of Hydrogen Energy, 2012, 37(11): 8929–8938
CrossRef
Google scholar
|
[41] |
Nie M, Shen P K, Wei Z. Nanocrystaline tungsten carbide supported Au-Pd electrocatalyst for oxygen reduction. Journal of Power Sources, 2007, 167(1): 69–73
CrossRef
Google scholar
|
[42] |
Meng H, Shen P K. Novel Pt-free catalyst for oxygen electroreduction. Electrochemistry Communications, 2006, 8(4): 588–594
CrossRef
Google scholar
|
[43] |
Meng H, Shen P K. The beneficial effect of the addition of tungsten carbides to Pt catalysts on the oxygen electroreduction. Chemical Communications, 2005, (35): 4408–4410
CrossRef
Google scholar
|
[44] |
Yu G Q, Huang B Y, Chen S M, Liao J W, Yin W J, Teobaldi G, Li X B. The combined role of faceting and heteroatom doping for hydrogen evolution on a WC electrocatalyst in aqueous solution: a density functional theory study. Journal of Physical Chemistry C, 2021, 125(8): 4602–4613
CrossRef
Google scholar
|
[45] |
Sulaiman J E, Zhu S, Xing Z, Chang Q, Shao M. Pt-Ni octahedra as electrocatalysts for the ethanol electro-oxidation reaction. ACS Catalysis, 2017, 7(8): 5134–5141
CrossRef
Google scholar
|
[46] |
Marcano D C, Kosynkin D V, Berlin J M, Sinitskii A, Sun Z, Slesarev A, Alemany L B, Lu W, Tour J M. Improved synthesis of graphene oxide. ACS Nano, 2010, 4(8): 4806–4814
CrossRef
Google scholar
|
[47] |
Kresse G, Hafner J. Ab initio molecular dynamics for liquid metals. Physical Review. B, 1993, 47(1): 558–561
CrossRef
Google scholar
|
[48] |
Kresse G, Furthmüller J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Computational Materials Science, 1996, 6(1): 15–50
CrossRef
Google scholar
|
[49] |
Perdew J P, Burke K, Ernzerhof M. Generalized gradient approximation made simple. Physical Review Letters, 1996, 77(18): 3865–3868
CrossRef
Google scholar
|
[50] |
Blöchl P E. Projector augmented-wave method. Physical Review. B, 1994, 50(24): 17953–17979
CrossRef
Google scholar
|
[51] |
Mukerjee S, Srinivasan S, Soriaga M P, McBreen J. Effect of preparation conditions of Pt alloys on their electronic, structural, and electrocatalytic activities for oxygen reduction-XRD, XAS, and electrochemical studies. Journal of Physical Chemistry, 1995, 99(13): 4577–4589
CrossRef
Google scholar
|
[52] |
Alov N V. Determination of the states of oxidation of metals in thin oxide films by X-ray photoelectron spectroscopy. Journal of Analytical Chemistry, 2005, 60(5): 431–435
CrossRef
Google scholar
|
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〈 |
|
〉 |