Platinum on nitrogen doped graphene and tungsten carbide supports for ammonia electro-oxidation reaction
Kumar Siddharth1, Yian Wang1, Jing Wang1,2, Fei Xiao1, Gabriel Sikukuu Nambafu1, Usman Bin Shahid1, Fei Yang1,2, Ernest Pahuyo Delmo1, Minhua Shao1,3,4()
1. Department of Chemical and Biological Engineering, The Hong Kong University of Science and Technology, Hong Kong, China 2. Department of Materials Science and Engineering, South University of Science and Technology of China, Shenzhen 518055, China 3. Southern Marine Science and Engineering Guangdong Laboratory (Guangzhou), The Hong Kong University of Science and Technology, Hong Kong, China 4. Chinese National Engineering Research Center for Control & Treatment of Heavy Metal Pollution, The Hong Kong University of Science and Technology, Hong Kong, China
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.
K Siddharth, Y Chan, L Wang, M Shao. Ammonia electro-oxidation reaction: recent development in mechanistic understanding and electrocatalyst design. Current Opinion in Electrochemistry, 2018, 9: 151–157 https://doi.org/10.1016/j.coelec.2018.03.011
2
Z F Li, Y Wang, G Botte. Revisiting the electrochemical oxidation of ammonia on carbon-supported metal nanoparticle catalysts. Electrochimica Acta, 2017, 228: 351–360 https://doi.org/10.1016/j.electacta.2017.01.020
3
B K Boggs, G Botte. On-board hydrogen storage and production: an application of ammonia electrolysis. Journal of Power Sources, 2009, 192(2): 573–581 https://doi.org/10.1016/j.jpowsour.2009.03.018
4
C Zhong, W B Hu, Y F Cheng. Recent advances in electrocatalysts for electro-oxidation of ammonia. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2013, 1(10): 3216–3238 https://doi.org/10.1039/C2TA00607C
5
Y T Chan, K Siddharth, M Shao. Investigation of cubic Pt alloys for ammonia oxidation reaction. Nano Research, 2020, 13(7): 1920–1927 https://doi.org/10.1007/s12274-020-2712-1
6
K Siddharth, Y Hong, X Qin, H J Lee, Y T Chan, S Zhu, G Chen, S I Choi, M Shao. Surface engineering in improving activity of Pt nanocubes for ammonia electrooxidation reaction. Applied Catalysis B: Environmental, 2020, 269: 118821 https://doi.org/10.1016/j.apcatb.2020.118821
7
K Siddharth, P Alam, M D Hossain, N Xie, G S Nambafu, F Rehman, J W Lam, G Chen, J Cheng, Z Luo, G Chen, B Z Tang, M Shao. Hydrazine detection during ammonia electro-oxidation using an aggregation-induced emission dye. Journal of the American Chemical Society, 2021, 143(5): 2433–2440 https://doi.org/10.1021/jacs.0c13178
R Abbasi, B P Setzler, J Wang, Y Zhao, T Wang, S Gottesfeld, Y Yan. Low-temperature direct ammonia fuel cells: recent developments and remaining challenges. Current Opinion in Electrochemistry, 2020, 21: 335–344 https://doi.org/10.1016/j.coelec.2020.03.021
J A Herron, P Ferrin, M Mavrikakis. Electrocatalytic oxidation of ammonia on transition-metal surfaces: a first-principles study. Journal of Physical Chemistry C, 2015, 119(26): 14692–14701 https://doi.org/10.1021/jp512981f
12
B K Boggs, G Botte. Optimization of Pt-Ir on carbon fiber paper for the electro-oxidation of ammonia in alkaline media. Electrochimica Acta, 2010, 55(19): 5287–5293 https://doi.org/10.1016/j.electacta.2010.04.040
13
E P Bonnin, E J Biddinger, G Botte. Effect of catalyst on electrolysis of ammonia effluents. Journal of Power Sources, 2008, 182(1): 284–290 https://doi.org/10.1016/j.jpowsour.2008.03.046
14
M Cooper, G Botte. 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 https://doi.org/10.1149/1.2240037
15
D A Daramola, G Botte. Theoretical study of ammonia oxidation on platinum clusters—adsorption of ammonia and water fragments. Computational & Theoretical Chemistry, 2012, 989: 7–17 https://doi.org/10.1016/j.comptc.2012.02.032
16
N V Rees, R G Compton. Carbon-free energy: a review of ammonia- and hydrazine-based electrochemical fuel cells. Energy & Environmental Science, 2011, 4(4): 1255–1260 https://doi.org/10.1039/c0ee00809e
17
N M Adli, H Zhang, S Mukherjee, G Wu. Ammonia oxidation electrocatalysis for hydrogen generation and fuel cells. Journal of the Electrochemical Society, 2018, 165(15): J3130–J3147 https://doi.org/10.1149/2.0191815jes
18
S Shanmugam, A Gedanken. Carbon‐coated anatase TiO2 nanocomposite as a high-performance electrocatalyst support. Small, 2007, 3(7): 1189–1193 https://doi.org/10.1002/smll.200600636
19
G S Chai, S B Yoon, J H Kim, J S Yu. 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 https://doi.org/10.1039/b412747c
20
G K Chandler, J D Genders, D Pletcher. Electrodes based on noble metals. Platinum Metals Review, 1997, 41(2): 54–63
21
F Takasaki, S Matsuie, Y Takabatake, Z Noda, A Hayashi, Y Shiratori, K Ito, K Sasaki. 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 https://doi.org/10.1149/1.3625918
22
S Jayabal, G Saranya, D Geng, L Y Lin, X Meng. 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 https://doi.org/10.1039/D0TA01530J
23
F J Vidal-Iglesias, J Solla-Gullón, V Montiel, J M Feliu, A Aldaz. 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 https://doi.org/10.1016/j.jpowsour.2007.06.015
24
X Wang, Q Kong, Y Han, Y Tang, X Wang, X Huang, T Lu. Construction of Ir-Co/C nanocomposites and their application in ammonia oxidation reaction. Journal of Electroanalytical Chemistry (Lausanne, Switzerland), 2019, 838: 101–106 https://doi.org/10.1016/j.jelechem.2019.02.044
25
T L Lomocso, E A Baranova. Electrochemical oxidation of ammonia on carbon-supported bi-metallic PtM (M= Ir, Pd, SnOx) nanoparticles. Electrochimica Acta, 2011, 56(24): 8551–8558 https://doi.org/10.1016/j.electacta.2011.07.041
26
S Samad, K S Loh, W Y Wong, T K Lee, J Sunarso, S T Chong, W R Daud. Carbon and non-carbon support materials for platinum-based catalysts in fuel cells. International Journal of Hydrogen Energy, 2018, 43(16): 7823–7854 https://doi.org/10.1016/j.ijhydene.2018.02.154
27
M Chen, J Liu, W Zhou, J Lin, Z Shen. Nitrogen-doped graphene-supported transition-metals carbide electrocatalysts for oxygen reduction reaction. Scientific Reports, 2015, 5(1): 1–10 https://doi.org/10.1038/srep10389
28
H Fei, J Dong, M J Arellano-Jiménez, G Ye, N Dong Kim, E L G Samuel, Z Peng, Z Zhu, F Qin, J Bao, M J Yacaman, P M Ajayan, D Chen, J M Tour. Atomic cobalt on nitrogen-doped graphene for hydrogen generation. Nature Communications, 2015, 6(1): 1–8 https://doi.org/10.1038/ncomms9668
29
C Zhang, J Sha, H Fei, M Liu, S Yazdi, J Zhang, Q Zhong, X Zou, N Zhao, H Yu, Z Jiang, E Ringe, B I Yakobson, J Dong, D Chen, J M Tour. Single-atomic ruthenium catalytic sites on nitrogen-doped graphene for oxygen reduction reaction in acidic medium. ACS Nano, 2017, 11(7): 6930–6941 https://doi.org/10.1021/acsnano.7b02148
30
G Wu, D Li, C Dai, D Wang, N Li. Well-dispersed high-loading Pt nanoparticles supported by shell-core nanostructured carbon for methanol electrooxidation. Langmuir, 2008, 24(7): 3566–3575 https://doi.org/10.1021/la7029278
31
X Lepró, E Terrés, Y Vega-Cantú, F J Rodríguez-Macías, H Muramatsu, Y A Kim, T Hayahsi, M Endo, M Torres, M Terrones. Efficient anchorage of Pt clusters on N-doped carbon nanotubes and their catalytic activity. Chemical Physics Letters, 2008, 463(1-3): 124–129 https://doi.org/10.1016/j.cplett.2008.08.001
32
H Chhina, S Campbell, O Kesler. 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 https://doi.org/10.1016/j.jpowsour.2007.12.105
33
D V Esposito, J G Chen. Monolayer platinum supported on tungsten carbides as low-cost electrocatalysts: opportunities and limitations. Energy & Environmental Science, 2011, 4(10): 3900–3912 https://doi.org/10.1039/c1ee01851e
34
R Ganesan, J S Lee. Tungsten carbide microspheres as a noble-metal-economic electrocatalyst for methanol oxidation. Angewandte Chemie International Edition, 2005, 44(40): 6557–6560 https://doi.org/10.1002/anie.200501272
35
H Meng, P K Shen. Tungsten carbide nanocrystal promoted Pt/C electrocatalysts for oxygen reduction. Journal of Physical Chemistry B, 2005, 109(48): 22705–22709 https://doi.org/10.1021/jp054523a
36
M Shao, B Merzougui, K Shoemaker, L Stolar, L Protsailo, Z J Mellinger, I J Hsu, J G Chen. Tungsten carbide modified high surface area carbon as fuel cell catalyst support. Journal of Power Sources, 2011, 196(18): 7426–7434 https://doi.org/10.1016/j.jpowsour.2011.04.026
37
Y Wang, S Song, V Maragou, P K Shen, P Tsiakaras. 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 https://doi.org/10.1016/j.apcatb.2008.11.032
38
J Zhang, J Chen, Y Jiang, F Zhou, G Wang, R Wang. Tungsten carbide encapsulated in nitrogen-doped carbon with iron/cobalt carbides electrocatalyst for oxygen reduction reaction. Applied Surface Science, 2016, 389: 157–164 https://doi.org/10.1016/j.apsusc.2016.07.071
39
H Hwu, J G Chen. Surface chemistry of transition metal carbides. Chemical Reviews, 2005, 105(1): 185–212 https://doi.org/10.1021/cr0204606
40
Y Liu, W E Mustain. Evaluation of tungsten carbide as the electrocatalyst support for platinum hydrogen evolution/oxidation catalysts. International Journal of Hydrogen Energy, 2012, 37(11): 8929–8938 https://doi.org/10.1016/j.ijhydene.2012.03.044
41
M Nie, P K Shen, Z Wei. Nanocrystaline tungsten carbide supported Au-Pd electrocatalyst for oxygen reduction. Journal of Power Sources, 2007, 167(1): 69–73 https://doi.org/10.1016/j.jpowsour.2006.12.059
H Meng, P K Shen. The beneficial effect of the addition of tungsten carbides to Pt catalysts on the oxygen electroreduction. Chemical Communications, 2005, (35): 4408–4410 https://doi.org/10.1039/b506900a
44
G Q Yu, B Y Huang, S M Chen, J W Liao, W J Yin, G Teobaldi, X B Li. 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 https://doi.org/10.1021/acs.jpcc.0c11104
45
J E Sulaiman, S Zhu, Z Xing, Q Chang, M Shao. Pt-Ni octahedra as electrocatalysts for the ethanol electro-oxidation reaction. ACS Catalysis, 2017, 7(8): 5134–5141 https://doi.org/10.1021/acscatal.7b01435
46
D C Marcano, D V Kosynkin, J M Berlin, A Sinitskii, Z Sun, A Slesarev, L B Alemany, W Lu, J M Tour. Improved synthesis of graphene oxide. ACS Nano, 2010, 4(8): 4806–4814 https://doi.org/10.1021/nn1006368
G Kresse, J Furthmüller. 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 https://doi.org/10.1016/0927-0256(96)00008-0
49
J P Perdew, K Burke, M Ernzerhof. Generalized gradient approximation made simple. Physical Review Letters, 1996, 77(18): 3865–3868 https://doi.org/10.1103/PhysRevLett.77.3865
S Mukerjee, S Srinivasan, M P Soriaga, J McBreen. 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 https://doi.org/10.1021/j100013a032
52
N V Alov. 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 https://doi.org/10.1007/s10809-005-0114-x
