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Research Article

Highly coordinated Pd overlayers on nanoporous gold for efficient formic acid electro-oxidation

Qinqin Sang1, Shuai Yin1, Feng Liu2, Huiming Yin1, Jia He1, Yi Ding1( )
Tianjin Key Laboratory of Advanced Functional Porous Materials,Institute for New Energy Materials & Low-Carbon Technologies, School of Materials Science and Engineering, Tianjin University of Technology,Tianjin,300384,China;
Kunming Institute of Precious Metals,Kunming,650106,China;
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Abstract

Design and fabrication of highly efficient and stable electrocatalysts remain key challenges in green energy technologies such as low-temperature direct liquid fuel cells. Based on in-depth theoretical calculations, here we demonstrate that surface Pd atoms with high coordination numbers (HCNs) can effectively modulate their adsorption energies for CO and OH, and thus achieve very high performance for formic acid electro-oxidation reaction (FAOR). Based on epitaxial coating Pd atomic layers onto nanoporous gold (NPG) thin membranes and a slight further decoration of Au clusters on top, the resulted core-shell structured NPG-Pd-Au electrocatalyst can demonstrate Pd intrinsic and mass activities of 8.62 mA·cm-2 and 27.25 A·mg-1 respectively at the peak potential around 0.33 V versus saturated calomel electrode toward FAOR, which are far better than those of commercial Pd/C catalysts (1.09 mA·cm-2 and 0.32 A·mg-1) tested under the same conditions. Moreover, the membrane electrode assemblies based on these low precious metal loading electrodes can achieve an anode Pd power efficiency over 10 W·mg-1 in a direct formic acid fuel cell, which is two orders of magnitude higher than that of the commercial Pd/C. These results provide new inspirations for the development of revolutionary electrodes for energy technologies in a rational manner.

Keywords

Pdnanoporous goldhigh coordination numberformic acid oxidationdirect formic acid fuel cell

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References

1

Mellmann, D.; Sponholz, P.; Junge, H.; Beller, M. Formic acid as a hydrogen storage material-development of homogeneous catalysts for selective hydrogen release. Chem. Soc. Rev. 2016, 45, 3954-3988.
Crossref Google Scholar
2

Eppinger, J.; Huang, K. W. Formic acid as a hydrogen energy carrier. ACS Energy Lett. 2017, 2, 188-195.
Crossref Google Scholar
3

Yang, X. C.; Pachfule, P.; Chen, Y.; Tsumori, N.; Xu, Q. Highly efficient hydrogen generation from formic acid using a reduced graphene oxide-supported AuPd nanoparticle catalyst. Chem. Commun. 2016, 52, 4171-4174.
Crossref Google Scholar
4

Zhan, C. Y.; Li, H. Q.; Li, X. M.; Jiang, Y. Q.; Xie, Z. X. Synthesis of PdH0.43 nanocrystals with different surface structures and their catalytic activities towards formic acid electro-oxidation. Sci. China Mater. 2020, 63, 375-382.
Crossref Google Scholar
5

Jiang, X.; Liu, Y.; Wang, J. X.; Wang, Y. F.; Xiong, Y. X.; Liu, Q.; Li, N. X.; Zhou, J. C.; Fu, G. T.; Sun, D. M. et al. 1-Naphthol induced Pt3Ag nanocorals as bifunctional cathode and anode catalysts of direct formic acid fuel cells. Nano Res. 2019, 12, 323-329.
Crossref Google Scholar
6

Rettenmaier, C.; Arán-Ais, R. M.; Timoshenko, J.; Rizo, R.; Jeon, H. S.; Kühl, S.; Chee, S. W.; Bergmann, A.; Cuenya, B. R. Enhanced formic acid oxidation over SnO2-decorated Pd nanocubes. ACS Catal. 2020, 10, 14540-14551.
Crossref Google Scholar
7

Espinosa, M. M. F.; Cheng, T.; Xu, M. J.; Abatemarco, L.; Choi, C.; Pan, X. Q.; Goddard Ⅲ, W. A.; Zhao, Z. P.; Huang, Y. Compressed intermetallic PdCu for enhanced electrocatalysis. ACS Energy Lett. 2020, 5, 3672-3680.
Crossref Google Scholar
8

Wang, Y. L.; Hu, P.; Yang, J.; Zhu, Y. A.; Chen, D. C-H bond activation in light alkanes: A theoretical perspective. Chem. Soc. Rev. 2021, 50, 4299-4358.
Crossref Google Scholar
9

Motagamwala, A. H.; Dumesic, J. A. Microkinetic modeling: A tool for rational catalyst design. Chem. Rev. 2021, 121, 1049-1076.
Crossref Google Scholar
10

Yoo, J. S.; Abild-Pedersen, F.; Nørskov, J. K.; Studt, F. Theoretical analysis of transition-metal catalysts for formic acid decomposition. ACS Catal. 2014, 4, 1226-1233.
Crossref Google Scholar
11

Wang, R. Y.; Liu, J. G.; Liu, P.; Bi, X. X.; Yan, X. L.; Wang, W. X.; Meng, Y. F.; Ge, X. B.; Chen, M. W.; Ding, Y. Ultra-thin layer structured anodes for highly durable low-Pt direct formic acid fuel cells. Nano Res. 2014, 7, 1569-1580.
Crossref Google Scholar
12

Yang, L.; Li, G. Q.; Chang, J. F.; Ge, J. J.; Liu, C. P.; Vladimir, F.; Wang, G. L.; Jin, Z.; Xing, W. Sea urchin-like Aucore@Pdshell electrocatalysts with high FAOR performance: Coefficient of lattice strain and electrochemical surface area. Appl. Catal. B: Environ. 2020, 260, 118200.
Crossref Google Scholar
13

Wang, L.; Chen, M. X.; Yan, Q. Q.; Xu, S. L.; Chu, S. Q.; Chen, P.; Lin, Y.; Liang, H. W. A sulfur-tethering synthesis strategy toward high-loading atomically dispersed noble metal catalysts. Sci. Adv. 2019, 5, eaax6322.
Crossref Google Scholar
14

Chaudhari, N. K.; Joo, J.; Kwon, H. B.; Kim, B.; Kim, H. Y.; Joo, S. H.; Lee, K. Nanodendrites of platinum-group metals for electrocatalytic applications. Nano Res. 2018, 11, 6111-6140.
Crossref Google Scholar
15

Xi, Z.; Li, J. R.; Su, D.; Muzzio, M.; Yu, C.; Li, Q.; Sun, S. H. Stabilizing CuPd nanoparticles via CuPd coupling to WO2.72 nanorods in electrochemical oxidation of formic acid. J. Am. Chem. Soc. 2017, 139, 15191-15196.
Crossref Google Scholar
16

Liu, Z. Y.; Fu, G. T.; Li, J. H.; Liu, Z. Q.; Xu, L.; Sun, D. M.; Tang, Y. W. Facile synthesis based on novel carbon-supported cyanogel of structurally ordered Pd3Fe/C as electrocatalyst for formic acid oxidation. Nano Res. 2018, 11, 4686-4696.
Crossref Google Scholar
17

Chang, J. F.; Feng, L. G.; Liu, C. P.; Xing, W.; Hu, X. L. An Effective Pd-Ni2P/C anode catalyst for direct formic acid fuel cells. Angew. Chem., Int. Ed. 2014, 53, 122-126.
Crossref Google Scholar
18

Liu, S. L.; Wang, Z. Q.; Zhang, H. G.; Yin, S. L.; Xu, Y.; Li, X. N.; Wang, L.; Wang, H. J. B-Doped PdRu nanopillar assemblies for enhanced formic acid oxidation electrocatalysis. Nanoscale 2020, 12, 19159-19164.
Crossref Google Scholar
19

Liu, D.; Xie, M. L.; Wang, C. M.; Liao, L. W.; Qiu, L.; Ma, J.; Huang, H.; Long, R.; Jiang, J.; Xiong, Y. J. Pd-Ag alloy hollow nanostructures with interatomic charge polarization for enhanced electrocatalytic formic acid oxidation. Nano Res. 2016, 9, 1590-1599.
Crossref Google Scholar
20

Liu, J. W.; Zheng, Y.; Hong, Z. L.; Cai, K.; Zhao, F.; Han, H. Y. Microbial synthesis of highly dispersed PdAu alloy for enhanced electrocatalysis. Sci. Adv. 2016, 2, e1600858.
Crossref Google Scholar
21

Guo, B. B.; Li, Q. L.; Lin, J.; Yu, C.; Gao, X. Q.; Fang, Y.; Liu, Z. Y.; Guo, Z. L.; Tang, C. C.; Huang, Y. Bimetallic AuPd nanoparticles loaded on amine-functionalized porous boron nitride nanofibers for catalytic dehydrogenation of formic acid. ACS Appl. Nano Mater. 2021, 4, 1849-1857.
Crossref Google Scholar
22

Hernández, A. R.; Estrada, E. M. A.; Ezeta, A.; Manríquez, M. E. Formic acid oxidation on AuPd core-shell electrocatalysts: Effect of surface electronic structure. Electrochim. Acta 2019, 327, 134977.
Crossref Google Scholar
23

Kibler, L. A.; El-Aziz, A. M.; Hoyer, R.; Kolb, D. M. Tuning reaction rates by lateral strain in a palladium monolayer. Angew. Chem., Int. Ed. 2005, 44, 2080-2084.
Crossref Google Scholar
24

Hu, S. Z.; Munoz, F.; Noborikawa, J.; Haan, J.; Scudiero, L.; Ha, S. Carbon supported Pd-based bimetallic and trimetallic catalyst for formic acid electrochemical oxidation. Appl. Catal. B: Environ. 2016, 180, 758-765.
Crossref Google Scholar
25

Lee, S. Y.; Jung, N.; Cho, J.; Park, H. Y.; Ryu, J.; Jang, I.; Kim, H. J.; Cho, E. A.; Park, Y. H.; Ham, H. C. et al. Surface-rearranged Pd3Au/C nanocatalysts by using CO-induced segregation for formic acid oxidation reactions. ACS Catal. 2014, 4, 2402-2408.
Crossref Google Scholar
26

Lee, J. H.; Cho, J.; Jeon, M.; Ridwan, M.; Park, H. S.; Choi, S. H.; Nam, S. W.; Han, J.; Lim, T. H.; Ham, H. C. et al. Experimental and computational studies of formic acid dehydrogenation over PdAu: Influence of ensemble and ligand effects on catalysis. J. Mater. Chem. A 2016, 4, 14141-14147.
Crossref Google Scholar
27

Liu, J. C.; Ma, X. L.; Li, Y.; Wang, Y. G.; Xiao, H.; Li, J. Heterogeneous Fe3 single-cluster catalyst for ammonia synthesis via an associative mechanism. Nat. Commun. 2018, 9, 1610.
Crossref Google Scholar
28

Hirshfeld, F. L. Bonded-atom fragments for describing molecular charge densities. Theor. Chim. Acta 1977, 44, 129-138.
Crossref Google Scholar
29

Liu, P.; Guan, P. F.; Hirata, A.; Zhang, L.; Chen, L. Y.; Wen, Y. R.; Ding, Y.; Fujita, T.; Erlebacher, J.; Chen, M. W. Visualizing under-coordinated surface atoms on 3D nanoporous gold catalysts. Adv. Mater. 2016, 28, 1753-1759.
Crossref Google Scholar
30

Wang, K. L.; Ding, Y. Carbon-free nanoporous gold based membrane electrocatalysts for fuel cells. Prog. Nat. Sci. : Mater. Int. 2020, 30, 775-786.
Crossref Google Scholar
31

Li, J.; Yin, H. M.; Li, X. B.; Okunishi, E.; Shen, Y. L.; He, J.; Tang, Z. K.; Wang, W. X.; Yücelen, E.; Li, C. et al. Surface evolution of a Pt-Pd-Au electrocatalyst for stable oxygen reduction. Nat. Energy 2017, 2, 17111.
Crossref Google Scholar
32

Jiang, X.; Xiong, Y. X.; Zhao, R. P.; Zhou, J. C.; Lee, J. M.; Tang, Y. W. Trimetallic Au@PdPb nanowires for oxygen reduction reaction. Nano Res. 2020, 13, 2691-2696.
Crossref Google Scholar
33

Lin, H. H.; Muzzio, M.; Wei, K. C.; Zhang, P.; Li, J. R.; Li, N.; Yin, Z. Y.; Su, D.; Sun, S. H. PdAu alloy nanoparticles for ethanol oxidation in alkaline conditions: Enhanced activity and C1 pathway selectivity. ACS Appl. Energy Mater. 2019, 2, 8701-8706.
Crossref Google Scholar
34

Wang, Z. L.; Liu, P.; Han, J. H.; Cheng, C.; Ning, S. C.; Hirata, A.; Fujita, T.; Chen, M. W. Engineering the internal surfaces of three-dimensional nanoporous catalysts by surfactant-modified dealloying. Nat. Commun. 2017, 8, 1066.
Crossref Google Scholar
35

Lu, X. L.; Yu, T. S.; Wang, H. L.; Qian, L. H.; Lei, P. X. Electrochemical fabrication and reactivation of nanoporous gold with abundant surface steps for CO2 reduction. ACS Catal. 2020, 10, 8860-8869.
Crossref Google Scholar
36

Zhou, Y.; Hu, X. C.; Fan, Q. Z.; Wen, H. R. Three-dimensional crumpled graphene as an electro-catalyst support for formic acid electro-oxidation. J. Mater. Chem. A 2016, 4, 4587-4591.
Crossref Google Scholar
37

Atkinson Ⅲ, R. W.; John, S. S.; Dyck, O.; Unocic, K. A.; Unocic, R. R.; Burke, C. S.; Cisco, J. W.; Rice, C. A.; Zawodzinski, T. A. Jr.; Papandrew, A. B. Supportless, bismuth-modified palladium nanotubes with improved activity and stability for formic acid oxidation. ACS Catal. 2015, 5, 5154-5163.
Crossref Google Scholar
38

Qiu, X. Y.; Zhang, H. Y.; Wu, P. S.; Zhang, F. Q.; Wei, S. H.; Sun, D. M.; Xu, L.; Tang, Y. W. One-pot synthesis of freestanding porous palladium nanosheets as highly efficient electrocatalysts for formic acid oxidation. Adv. Funct. Mater. 2017, 27, 1603852.
Crossref Google Scholar
39

Fan, X. L.; Yuan, W. Y.; Zhang, D. H.; Li, C. M. Heteropolyacid-mediated self-assembly of heteropolyacid-modified pristine graphene supported Pd nanoflowers for superior catalytic performance toward formic acid oxidation. ACS Appl. Energy Mater. 2018, 1, 411-420.
Crossref Google Scholar
40

Bin, D.; Yang, B. B.; Ren, F. F.; Zhang, K.; Yang, P.; Du, Y. K. Facile synthesis of PdNi nanowire networks supported on reduced graphene oxide with enhanced catalytic performance for formic acid oxidation. J. Mater. Chem. A 2015, 3, 14001-14006.
Crossref Google Scholar
41

Lai, J. P.; Niu, W. X.; Li, S. P.; Wu, F. X.; Luque, R.; Xu, G. B. Concave and duck web-like platinum nanopentagons with enhanced electrocatalytic properties for formic acid oxidation. J. Mater. Chem. A 2016, 4, 807-812.
Crossref Google Scholar
42

Li, Z.; Chen, Y. J.; Ji, S. F.; Tang, Y.; Chen, W. X.; Li, A.; Zhao, J.; Xiong, Y.; Wu, Y. E.; Gong, Y. et al. Iridium single-atom catalyst on nitrogen-doped carbon for formic acid oxidation synthesized using a general host-guest strategy. Nat. Chem. 2020, 12, 764-772.
Crossref Google Scholar
43

Xiong, Y.; Dong, J. C.; Huang, Z. Q.; Xin, P. Y.; Chen, W. X.; Wang, Y.; Li, Z.; Jin, Z.; Xing, W.; Zhuang, Z. B. et al. Single-atom Rh/N-doped carbon electrocatalyst for formic acid oxidation. Nat. Nanotechnol. 2020, 15, 390-397.
Crossref Google Scholar
44

Xu, Y.; Yu, S. S.; Ren, T. L.; Li, C. J.; Yin, S. L.; Wang, Z. Q.; Li, X. N.; Wang, L.; Wang, H. J. A quaternary metal-metalloid-nonmetal electrocatalyst: B, P-co-doping into PdRu nanospine assemblies boosts the electrocatalytic capability toward formic acid oxidation. J. Mater. Chem. A 2020, 8, 2424-2429.
Crossref Google Scholar
45

Xu, H.; Zhang, K.; Yan, B.; Wang, J.; Wang, C. Q.; Li, S. M.; Gu, Z. L.; Du, Y. K.; Yang, P. Ultra-uniform PdBi nanodots with high activity towards formic acid oxidation. J. Power Sources 2017, 356, 27-35.
Crossref Google Scholar
46

Zhang, L. Y.; Ouyang, Y. R.; Wang, S.; Wu, D. B.; Jiang, M. C.; Wang, F. Q.; Yuan, W. Y.; Li, C. M. Perforated Pd nanosheets with crystalline/amorphous heterostructures as a highly active robust catalyst toward formic acid oxidation. Small 2019, 15, 1904245.
Crossref Google Scholar
47

Ding, J.; Liu, Z.; Liu, X. R.; Liu, J.; Deng, Y. D.; Han, X. P.; Zhong, C.; Hu, W. B. Mesoporous decoration of freestanding palladium nanotube arrays boosts the electrocatalysis capabilities toward formic acid and formate oxidation. Adv. Energy Mater. 2019, 9, 1900955.
Crossref Google Scholar
48

Ding, J.; Liu, Z.; Liu, X. R.; Liu, B.; Liu, J.; Deng, Y. D.; Han, X. P.; Hu, W. B.; Zhong, C. Tunable periodically ordered mesoporosity in palladium membranes enables exceptional enhancement of intrinsic electrocatalytic activity for formic acid oxidation. Angew. Chem., Int. Ed. 2020, 59, 5092-5101.
Crossref Google Scholar
49

Yang, N. L.; Zhang, Z. C.; Chen, B.; Huang, Y.; Chen, J. Z.; Lai, Z. C.; Chen, Y.; Sindoro, M.; Wang, A. L.; Cheng, H. F. et al. Synthesis of ultrathin PdCu alloy nanosheets used as a highly efficient electrocatalyst for formic acid oxidation. Adv. Mater. 2017, 29, 1700769.
Crossref Google Scholar
Nano Research
Volume 14 Issue 10,
October 2021
Pages 3502-3508
DOI: 10.1007/s12274-021-3642-2
Cite this article:
Sang Q, Yin S, Liu F, et al. Highly coordinated Pd overlayers on nanoporous gold for efficient formic acid electro-oxidation. Nano Research, 2021, 14(10): 3502-3508. https://doi.org/10.1007/s12274-021-3642-2
Topics:
Catalysis

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Received: 15 March 2021
Revised: 21 May 2021
Accepted: 02 June 2021
Published: 28 June 2021
© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2021
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