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Nano Research 2023, 16(2): 2366-2372 https://doi.org/10.1007/s12274-022-4891-4
Research Article | Issue | Published: 30 August 2022

The promoting effect of interstitial hydrogen on the oxygen reduction performance of PtPd alloy nanotubes for fuel cells

Show Author's Information Tingting Chao1,§,  Xuan Luo2,§,  Mengzhao Zhu1,§,  Yanmin Hu1,  Yida Zhang3,  Yunteng Qu1,  Hantao Peng4,  Xiaoshuang Shen5,  Xusheng Zheng3,  Liang Zhang2( ),  Xun Hong1( )
Center of Advanced Nanocatalysis (CAN), Department of Applied Chemistry, University of Science and Technology of China, Hefei 230026, China
Country Center for Combustion Energy and School of Vehicle and Mobility, Tsinghua University, Beijing 100084, China
National Synchrotron Radiation Laboratory (NSRL), University of Science and Technology of China, Hefei 230029, China
Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China
School of Physical Science and Technology, Yangzhou University, Yangzhou 225002, China

§ Tingting Chao, Xuan Luo, and Mengzhao Zhu contributed equally to this work.

Keywords:
oxygen reduction reaction, alloy, fuel cell, hydrogen atoms incorporation, d-band structure regulation
Topics:
Fuel cellsOxygen reduction reaction
Cite this article:
Chao T, Luo X, Zhu M, et al. The promoting effect of interstitial hydrogen on the oxygen reduction performance of PtPd alloy nanotubes for fuel cells. Nano Research, 2023, 16(2): 2366-2372. https://doi.org/10.1007/s12274-022-4891-4
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Abstract Full text Electronic supplementary material About this article

Highly efficient and stable oxygen reduction reaction (ORR) electrocatalysts are remarkably important but challenging for advancing the large-scale commercialization of practical proton exchange membrane fuel cells (PEMFCs). In this work, we report that the introduction of interstitial hydrogen atoms into PtPd nanotubes can significantly promote ORR performance without scarifying the durability. The enhanced mass activity was 8.8 times higher than that of commercial Pt/C. The accelerated durability test showed negligible activity attenuation after 30,000 cycles. Additionally, H2/O2 fuel cell tests further verified the excellent activity of PtPd-H nanotubes with a maximum power density of 1.32 W·cm−2, superior to that of commercial Pt/C (1.16 W·cm−2). Density functional theory calculations demonstrated the incorporation of hydrogen atoms gives rise to the broadening of Pt d-band and the downshift of d-band center, which consequently leads to the weaker intermediates binding and enhanced ORR activity.


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About this article

The promoting effect of interstitial hydrogen on the oxygen reduction performance of PtPd alloy nanotubes for fuel cells

Show Author's information Tingting Chao1,§, Xuan Luo2,§, Mengzhao Zhu1,§, Yanmin Hu1, Yida Zhang3, Yunteng Qu1, Hantao Peng4, Xiaoshuang Shen5, Xusheng Zheng3, Liang Zhang2( ), Xun Hong1( )
Center of Advanced Nanocatalysis (CAN), Department of Applied Chemistry, University of Science and Technology of China, Hefei 230026, China
Country Center for Combustion Energy and School of Vehicle and Mobility, Tsinghua University, Beijing 100084, China
National Synchrotron Radiation Laboratory (NSRL), University of Science and Technology of China, Hefei 230029, China
Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China
School of Physical Science and Technology, Yangzhou University, Yangzhou 225002, China

§ Tingting Chao, Xuan Luo, and Mengzhao Zhu contributed equally to this work.

Abstract

Highly efficient and stable oxygen reduction reaction (ORR) electrocatalysts are remarkably important but challenging for advancing the large-scale commercialization of practical proton exchange membrane fuel cells (PEMFCs). In this work, we report that the introduction of interstitial hydrogen atoms into PtPd nanotubes can significantly promote ORR performance without scarifying the durability. The enhanced mass activity was 8.8 times higher than that of commercial Pt/C. The accelerated durability test showed negligible activity attenuation after 30,000 cycles. Additionally, H2/O2 fuel cell tests further verified the excellent activity of PtPd-H nanotubes with a maximum power density of 1.32 W·cm−2, superior to that of commercial Pt/C (1.16 W·cm−2). Density functional theory calculations demonstrated the incorporation of hydrogen atoms gives rise to the broadening of Pt d-band and the downshift of d-band center, which consequently leads to the weaker intermediates binding and enhanced ORR activity.

Keywords: oxygen reduction reaction, alloy, fuel cell, hydrogen atoms incorporation, d-band structure regulation

References(40)

[1]

Stephens, I. E. L.; Rossmeisl, J.; Chorkendorff, I. Toward sustainable fuel cells. Science 2016, 354, 1378–1379.
DOI Google Scholar
[2]

Weydahl, H.; Gilljam, M.; Lian, T.; Johannessen, T. C.; Holm, S. I.; Hasvold, J. Ø. Fuel cell systems for long-endurance autonomous underwater vehicles—Challenges and benefits. Int. J. Hydrog. Energy 2020, 45, 5543–5553.
DOI Google Scholar
[3]

Wang, X. X.; Swihart, M. T.; Wu, G. Achievements, challenges and perspectives on cathode catalysts in proton exchange membrane fuel cells for transportation. Nat. Catal. 2019, 2, 578–589.
DOI Google Scholar
[4]

Greeley, J.; Stephens, I. E. L.; Bondarenko, A. S.; Johansson, T. P.; Hansen, H. A.; Jaramillo, T. F.; Rossmeisl, J.; Chorkendorff, I.; Nørskov, J. K. Alloys of platinum and early transition metals as oxygen reduction electrocatalysts. Nat. Chem. 2009, 1, 552–556.
DOI Google Scholar
[5]

Jing, H. Y.; Zhu, P.; Zheng, X. B.; Zhang, Z. D.; Wang, D. S.; Li, Y. D. Theory-oriented screening and discovery of advanced energy transformation materials in electrocatalysis. Adv. Powder Mater. 2022, 1, 100013.
DOI Google Scholar
[6]

Hu, Y. M.; Zhu, M. Z.; Luo, X.; Wu, G.; Chao, T. T.; Qu, Y. T.; Zhou, F. Y.; Sun, R. B.; Han, X.; Li, H. et al. Coplanar Pt/C nanomeshes with ultrastable oxygen reduction performance in fuel cells. Angew. Chem., Int. Ed. 2021, 60, 6533–6538.
DOI Google Scholar
[7]

Han, A.; Wang, X. J.; Tang, K.; Zhang, Z. D.; Ye, C. L.; Kong, K. J.; Hu, H. B.; Zheng, L. R.; Jiang, P.; Zhao, C. X. et al. An adjacent atomic platinum site enables single-atom iron with high oxygen reduction reaction performance. Angew. Chem., Int. Ed. 2021, 60, 19262–19271.
DOI Google Scholar
[8]

Wang, Y.; Zheng, M.; Li, Y. R.; Ye, C. L.; Chen, J.; Ye, J. Y.; Zhang, Q. H.; Li, J.; Zhou, Z. Y.; Fu, X. Z. et al. p–d orbital hybridization induced by a monodispersed Ga site on a Pt3Mn nanocatalyst boosts ethanol electrooxidation. Angew. Chem., Int. Ed. 2022, 134, e202115735.
DOI Google Scholar
[9]

Cui, T. T.; Wang, Y. P.; Ye, T.; Wu, J.; Chen, Z. Q.; Li, J.; Lei, Y. P.; Wang, D. S.; Li, Y. D. Engineering dual single-atom sites on 2D ultrathin N-doped carbon nanosheets attaining ultra-low-temperature zinc-air battery. Angew. Chem., Int. Ed. 2022, 61, e202115219.
DOI Google Scholar
[10]

Zhu, P.; Xiong, X.; Wang, D. S. Regulations of active moiety in single atom catalysts for electrochemical hydrogen evolution reaction. Nano Res. 2022, 15, 5792–5815.
DOI Google Scholar
[11]

Chen, Y. J.; Gao, R.; Ji, S. F.; Li, H. J.; Tang, K.; Jiang, P.; Hu, H. B.; Zhang, Z. D.; Hao, H. H.; Qu, Q. Y. et al. Atomic-level modulation of electronic density at cobalt single-atom sites derived from metal-organic frameworks: Enhanced oxygen reduction performance. Angew. Chem., Int. Ed. 2021, 60, 3212–3221.
DOI Google Scholar
[12]

Tian, X. L.; Zhao, X.; Su, Y. Q.; Wang, L. J.; Wang, H. M.; Dang, D.; Chi, B.; Liu, H. F.; Hensen, E. J. M.; Lou, X. W. et al. Engineering bunched Pt-Ni alloy nanocages for efficient oxygen reduction in practical fuel cells. Science 2019, 366, 850–856.
DOI Google Scholar
[13]

Wu, Z. P.; Caracciolo, D. T.; Maswadeh, Y.; Wen, J. G.; Kong, Z. J.; Shan, S. Y.; Vargas, J. A.; Yan, S.; Hopkins, E.; Park, K. et al. Alloying–realloying enabled high durability for Pt–Pd-3d-transition metal nanoparticle fuel cell catalysts. Nat. Commun. 2021, 12, 859.
DOI Google Scholar
[14]

Chen, S.; Zhao, J. K.; Su, H. Y.; Li, H. L.; Wang, H. L.; Hu, Z. P.; Bao, J.; Zeng, J. Pd–Pt tesseracts for the oxygen reduction reaction. J. Am. Chem. Soc. 2021, 143, 496–503.
DOI Google Scholar
[15]

Wang, X.; Choi, S. I.; Roling, L. T.; Luo, M.; Ma, C.; Zhang, L.; Chi, M. F.; Liu, J. Y.; Xie, Z. X.; Herron, J. A. et al. Palladium–platinum core–shell icosahedra with substantially enhanced activity and durability towards oxygen reduction. Nat. Commun. 2015, 6, 7594.
DOI Google Scholar
[16]

Sasaki, K.; Naohara, H.; Cai, Y.; Choi, Y. M.; Liu, P.; Vukmirovic, M. B.; Wang, J. X.; Adzic, R. R. Core-protected platinum monolayer shell high-stability electrocatalysts for fuel-cell cathodes. Angew. Chem., Int. Ed. 2010, 49, 8602–8607.
DOI Google Scholar
[17]

Lu, B. A.; Shen, L. F.; Liu, J.; Zhang, Q. H.; Wan, L. Y.; Morris, D. J.; Wang, R. X.; Zhou, Z. Y.; Li, G.; Sheng, T. et al. Structurally disordered phosphorus-doped Pt as a highly active electrocatalyst for an oxygen reduction reaction. ACS Catal. 2020, 11, 355–363.
DOI Google Scholar
[18]

Guo, Q.; Chen, R. T.; Guo, J. P.; Qin, C.; Xiong, Z. T.; Yan, H. X.; Gao, W. B.; Pei, Q. J.; Wu, A. A.; Chen, P. Enabling semihydrogenation of alkynes to alkenes by using a calcium palladium complex hydride. J. Am. Chem. Soc. 2021, 143, 20891–20897.
DOI Google Scholar
[19]

Kobayashi, K.; Kobayashi, H.; Maesato, M.; Hayashi, M.; Yamamoto, T.; Yoshioka, S.; Matsumura, S.; Sugiyama, T.; Kawaguchi, S.; Kubota, Y. et al. Discovery of hexagonal structured Pd–B nanocrystals. Angew. Chem., Int. Ed. 2017, 56, 6578–6582.
DOI Google Scholar
[20]

Chen, T. Y.; Ellis, I.; Hooper, T. J. N.; Liberti, E.; Ye, L.; Lo, B. T. W.; O’Leary, C.; Sheader, A. A.; Martinez, G. T.; Jones, L. et al. Interstitial boron atoms in the palladium lattice of an industrial type of nanocatalyst: Properties and structural modifications. J. Am. Chem. Soc. 2019, 141, 19616–19624.
DOI Google Scholar
[21]
Zheng, X. B.; Li, B. B.; Wang, Q. S.; Wang, D. S.; Li, Y. D. Emerging low-nuclearity supported metal catalysts with atomic level precision for efficient heterogeneous catalysis. Nano Res. 2022, in press, https://doi.org./10.1007/s12274-022-4429-9.
[22]

Hong, J.; Bae, J. H.; Jo, H.; Park, H. Y.; Lee, S.; Hong, S. J.; Chun, H.; Cho, M. K.; Kim, J.; Kim, J. et al. Metastable hexagonal close-packed palladium hydride in liquid cell TEM. Nature 2022, 603, 631–636.
DOI Google Scholar
[23]

Chen, T. Y.; Foo, C.; Tsang, S. C. E. Interstitial and substitutional light elements in transition metals for heterogeneous catalysis. Chem. Sci. 2021, 12, 517–532.
DOI Google Scholar
[24]

Li, R. Z.; Wang, D. S. Understanding the structure-performance relationship of active sites at atomic scale. Nano Res. 2022, 15, 6888–6923.
DOI Google Scholar
[25]

Ai, X.; Zou, X.; Chen, H.; Su, Y. T.; Feng, X. L.; Li, Q. J.; Liu, Y. P.; Zhang, Y.; Zou, X. X. Transition-metal-boron intermetallics with strong interatomic d–sp orbital hybridization for high-performance electrocatalysis. Angew. Chem., Int. Ed. 2020, 59, 3961–3965.
DOI Google Scholar
[26]

Vo Doan, T. T.; Wang, J. B.; Poon, K. C.; Tan, D. C. L.; Khezri, B.; Webster, R. D.; Su, H. B.; Sato, H. Theoretical modelling and facile synthesis of a highly active boron-doped palladium catalyst for the oxygen reduction reaction. Angew. Chem., Int. Ed. 2016, 55, 6842–6847.
DOI Google Scholar
[27]

Fan, J. C.; Wu, J. D.; Cui, X. Q.; Gu, L.; Zhang, Q. H.; Meng, F. Q.; Lei, B. H.; Singh, D. J.; Zheng, W. T. Hydrogen stabilized RhPdH 2D bimetallene nanosheets for efficient alkaline hydrogen evolution. J. Am. Chem. Soc. 2020, 142, 3645–3651.
DOI Google Scholar
[28]

Dekura, S.; Kobayashi, H.; Ikeda, R.; Maesato, M.; Yoshino, H.; Ohba, M.; Ishimoto, T.; Kawaguchi, S.; Kubota, Y.; Yoshioka, S. et al. The electronic state of hydrogen in the α phase of the hydrogen-storage material PdH(D)x: Does a chemical bond between palladium and hydrogen exist? Angew. Chem., Int. Ed. 2018, 57, 9823–9827.
DOI Google Scholar
[29]

Kim, J.; Kim, H.; Lee, W. J.; Ruqia, B.; Baik, H.; Oh, H. S.; Paek, S. M.; Lim, H. K.; Choi, C. H.; Choi, S. I. Theoretical and experimental understanding of hydrogen evolution reaction kinetics in alkaline electrolytes with Pt-based core–shell nanocrystals. J. Am. Chem. Soc. 2019, 141, 18256–18263.
DOI Google Scholar
[30]

Lu, Y. Z.; Wang, J.; Peng, Y. C.; Fisher, A.; Wang, X. Highly efficient and durable Pd hydride nanocubes embedded in 2D amorphous NiB nanosheets for oxygen reduction reaction. Adv. Energy Mater. 2017, 7, 1700919.
DOI Google Scholar
[31]

Shi, Y. F.; Schimmenti, R.; Zhu, S. Q.; Venkatraman, K.; Chen, R. H.; Chi, M. F.; Shao, M. H.; Mavrikakis, M.; Xia, Y. N. Solution-phase synthesis of PdH0.706 nanocubes with enhanced stability and activity toward formic acid oxidation. J. Am. Chem. Soc. 2022, 144, 2556–2568.
DOI Google Scholar
[32]

Li, H. Q.; Zeng, R.; Feng, X. R.; Wang, H. S.; Xu, W. X.; Lu, X. Y.; Xie, Z. X.; Abruña, H. D. Oxidative stability matters: A case study of palladium hydride nanosheets for alkaline fuel cells. J. Am. Chem. Soc. 2022, 144, 8106–8114.
DOI Google Scholar
[33]

Lin, B. Q.; Wu, X.; Xie, L.; Kang, Y. Q.; Du, H. D.; Kang, F. Y.; Li, J.; Gan, L. Atomic imaging of subsurface interstitial hydrogen and insights into surface reactivity of palladium hydrides. Angew. Chem., Int. Ed. 2020, 59, 20348–20352.
DOI Google Scholar
[34]

Zhao, Z. P.; Huang, X. Q.; Li, M. F.; Wang, G. M.; Lee, C.; Zhu, E. B.; Duan, X. F.; Huang, Y. Synthesis of stable shape-controlled catalytically active β-palladium hydride. J. Am. Chem. Soc. 2015, 137, 15672–15675.
DOI Google Scholar
[35]

Dai, Y.; Mu, X. L.; Tan, Y. M.; Lin, K. Q.; Yang, Z. L; Zheng, N. F.; Fu G. Carbon monoxide-assisted synthesis of single-crystalline Pd tetrapod nanocrystals through hydride formation. J. Am. Chem. Soc. 2012, 134, 7073–7080.
DOI Google Scholar
[36]

Xu, W. C.; Fan, G. L.; Chen, J. L.; Li, J. H.; Zhang, L.; Zhu, S. L.; Su, X. C.; Cheng, F. Y.; Chen, J. Nanoporous palladium hydride for electrocatalytic N2 reduction under ambient conditions. Angew. Chem., Int. Ed. 2020, 59, 3511–3516.
DOI Google Scholar
[37]

Narayan, T. C.; Baldi, A.; Koh, A. L.; Sinclair, R.; Dionne, J. A. Reconstructing solute-induced phase transformations within individual nanocrystals. Nat. Mater. 2016, 15, 768–774.
DOI Google Scholar
[38]

Fan, J. C.; Cui, X. Q.; Yu, S. S.; Gu, L.; Zhang, Q. H.; Meng, F. Q.; Peng, Z. Q.; Ma, L. O.; Ma, J. Y.; Qi, K. et al. Interstitial hydrogen atom modulation to boost hydrogen evolution in Pd-based alloy nanoparticles. ACS Nano 2019, 13, 12987–12995.
DOI Google Scholar
[39]

Nørskov, J. K.; Rossmeisl, J.; Logadottir, A.; Lindqvist, L.; Kitchin, J. R.; Bligaard, T.; Jónsson, H. Origin of the overpotential for oxygen reduction at a fuel-cell cathode. J. Phys. Chem. B 2004, 108, 17886–17892.
DOI Google Scholar
[40]

Greeley, J.; Nørskov, J. K. A general scheme for the estimation of oxygen binding energies on binary transition metal surface alloys. Surf. Sci. 2005, 592, 104–111.
DOI Google Scholar
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Acknowledgements

Publication history

Received: 17 June 2022
Revised: 08 August 2022
Accepted: 09 August 2022
Published: 30 August 2022
Issue date: February 2023

Copyright

© Tsinghua University Press 2022

Acknowledgements

Acknowledgements

This work was supported by the National Key R&D Program of China (Nos. 2017YFA0700104 and 2018YFA0702001), the National Natural Science Foundation of China (No. 21871238), the Fundamental Research Funds for the Central Universities (No. WK2060000016), the Youth Innovation Promotion Association of the Chinese Academy of Science (No. 2018494), and the Hefei National Laboratory for Physical Sciences at the Microscale (No. KF2020107).

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