Journal Home > Volume 9 , Issue 6
Nano Research 2016, 9(6): 1590-1599 https://doi.org/10.1007/s12274-016-1053-6
Research Article | Issue | Published: 31 March 2016

Pd-Ag alloy hollow nanostructures with interatomic charge polarization for enhanced electrocatalytic formic acid oxidation

Show Author's Information Dong Liu1,§,  Maolin Xie1,§,  Chengming Wang1( ),  Lingwen Liao2,  Lu Qiu1,  Jun Ma1,  Hao Huang1,  Ran Long1,  Jun Jiang1( ),  Yujie Xiong1( )
Hefei National Laboratory for Physical Sciences at the MicroscaleiChEM (Collaborative Innovation Center of Chemistry for Energy Materials)Hefei Science Center (CAS)and School of Chemistry and Materials ScienceUniversity of Science and Technology of ChinaHefei230026China
Key Laboratory of Materials PhysicsInstitute of Solid State PhysicsChinese Academy of SciencesHefei230021China

§ These authors contributed equally to this work.

Keywords:
palladium, silver, electrocatalysis, formic acid oxidation, hollow nanostructures
Cite this article:
Liu D, Xie M, Wang C, et al. Pd-Ag alloy hollow nanostructures with interatomic charge polarization for enhanced electrocatalytic formic acid oxidation. Nano Research, 2016, 9(6): 1590-1599. https://doi.org/10.1007/s12274-016-1053-6
Download citation
EndNote(RIS)
BibTeX

860

Views

21

Downloads

Citations

100

Crossref

N/A

WoS

100

Scopus

15

CSCD

Abstract Full text Electronic supplementary material About this article

Formic acid oxidation is an important electrocatalytic reaction in proton-exchange membrane (PEM) fuel cells, in which both active sites and species adsorption/activation play key roles. In this study, we have developed hollow Pd-Ag alloy nanostructures with high active surface areas for application to electrocatalytic formic acid oxidation. When a certain amount of Ag is incorporated into a Pd lattice, which is already a highly active material for formic acid oxidation, the electrocatalytic activity can be significantly boosted. As indicated by theoretical simulations, coupling between Pd and Ag induces polarization charges on Pd catalytic sites, which can enhance the adsorption of HCOO* species. As a result, the designed electrocatalysts can achieve reduced Pd usage and enhanced catalytic properties at the same time. This study represents an approach that simultaneously fabricates hollow structures to increase the number of active sites and utilizes interatomic interactions to tune species adsorption/activation towards improved electrocatalytic performance.


menu
Abstract
Full text
Outline
Electronic supplementary material
About this article

Pd-Ag alloy hollow nanostructures with interatomic charge polarization for enhanced electrocatalytic formic acid oxidation

Show Author's information Dong Liu1,§, Maolin Xie1,§, Chengming Wang1( ), Lingwen Liao2, Lu Qiu1, Jun Ma1, Hao Huang1, Ran Long1, Jun Jiang1( ), Yujie Xiong1( )
Hefei National Laboratory for Physical Sciences at the MicroscaleiChEM (Collaborative Innovation Center of Chemistry for Energy Materials)Hefei Science Center (CAS)and School of Chemistry and Materials ScienceUniversity of Science and Technology of ChinaHefei230026China
Key Laboratory of Materials PhysicsInstitute of Solid State PhysicsChinese Academy of SciencesHefei230021China

§ These authors contributed equally to this work.

Abstract

Formic acid oxidation is an important electrocatalytic reaction in proton-exchange membrane (PEM) fuel cells, in which both active sites and species adsorption/activation play key roles. In this study, we have developed hollow Pd-Ag alloy nanostructures with high active surface areas for application to electrocatalytic formic acid oxidation. When a certain amount of Ag is incorporated into a Pd lattice, which is already a highly active material for formic acid oxidation, the electrocatalytic activity can be significantly boosted. As indicated by theoretical simulations, coupling between Pd and Ag induces polarization charges on Pd catalytic sites, which can enhance the adsorption of HCOO* species. As a result, the designed electrocatalysts can achieve reduced Pd usage and enhanced catalytic properties at the same time. This study represents an approach that simultaneously fabricates hollow structures to increase the number of active sites and utilizes interatomic interactions to tune species adsorption/activation towards improved electrocatalytic performance.

Keywords: palladium, silver, electrocatalysis, formic acid oxidation, hollow nanostructures

References(39)

1

Iyyamperumal, R.; Zhang, L.; Henkelman, G.; Crooks, R. M. Efficient electrocatalytic oxidation of formic acid using Au@Pt dendrimer-encapsulated nanoparticles. J. Am. Chem. Soc. 2013, 135, 5521–5524.
DOI Google Scholar
2

Ma, L.; Wang, C. M.; Gong, M.; Liao, L. W.; Long, R.; Wang, J. G.; Wu, D.; Zhong, W.; Kim, M. J.; Chen, Y. X. et al. Control over the branched structures of platinum nanocrystals for electrocatalytic applications. ACS Nano 2012, 6, 9797–9806.
DOI Google Scholar
3

Zhang, S.; Shao, Y. Y.; Yin, G. P.; Lin, Y. H. Electrostatic self-assembly of a Pt-around-Au nanocomposite with high activity towards formic acid oxidation. Angew. Chem., Int. Ed. 2010, 49, 2211–2214.
DOI Google Scholar
4

Scofield, M. E.; Koenigsmann, C.; Wang, L.; Liu, H. Q.; Wong, S. S. Tailoring the composition of ultrathin, ternary alloy PtRuFe nanowires for the methanol oxidation reaction and formic acid oxidation reaction. Energy Environ. Sci. 2015, 8, 350–363.
DOI Google Scholar
5

Fu, G. T.; Xia, B. Y.; Ma, R. G.; Chen, Y.; Tang, Y. W.; Lee, J. M. Trimetallic PtAgCu@PtCu core@shell concave nanooctahedrons with enhanced activity for formic acid oxidation reaction. Nano Energy 2015, 12, 824–832.
DOI Google Scholar
6

Zhang, H.; Jin, M. S.; Xia, Y. N. Enhancing the catalytic and electrocatalytic properties of Pt-based catalysts by forming bimetallic nanocrystals with Pd. Chem. Soc. Rev. 2012, 41, 8035–8049.
DOI Google Scholar
7

Jin, M. S.; Zhang, H.; Xie, Z. X.; Xia, Y. N. Palladium nanocrystals enclosed by {100} and {111} facets in controlled proportions and their catalytic activities for formic acid oxidation. Energy Environ. Sci. 2012, 5, 6352–6357.
DOI Google Scholar
8

Mazumder, V.; Sun, S. H. Oleylamine-mediated synthesis of Pd nanoparticles for catalytic formic acid oxidation. J. Am. Chem. Soc. 2009, 131, 4588–4589.
DOI Google Scholar
9

Xia, X. H.; Choi, S. I.; Herron, J. A.; Lu, N.; Scaranto, J.; Peng, H. C.; Wang, J. G.; Mavrikakis, M.; Kim, M. J.; Xia, Y. N. Facile synthesis of palladium right bipyramids and their use as seeds for overgrowth and as catalysts for formic acid oxidation. J. Am. Chem. Soc. 2013, 135, 15706–15709.
DOI Google Scholar
10

Su, N.; Chen, X. Y.; Ren, Y. H.; Yue, B.; Wang, H.; Cai, W. B.; He, H. Y. The facile synthesis of single crystalline palladium arrow-headed tripods and their application in formic acid electro-oxidation. Chem. Commun. 2015, 51, 7195–7198.
DOI Google Scholar
11

Zheng, J. N.; Zhang, M.; Li, F. F.; Li, S. S.; Wang, A. J.; Feng, J. J. Facile synthesis of Pd nanochains with enhanced electrocatalytic performance for formic acid oxidation. Electrochim. Acta 2014, 130, 446–452.
DOI Google Scholar
12

Lu, Y. Z.; Chen, W. Nanoneedle-covered Pd-Ag nanotubes: High electrocatalytic activity for formic acid oxidation. J. Phys. Chem. C 2010, 114, 21190–21200.
DOI Google Scholar
13

Mazumder, V.; Chi, M. F.; Mankin, M. N.; Liu, Y.; Metin, Ö.; Sun, D. H.; More, K. L.; Sun, S. H. A facile synthesis of MPd (M = Co, Cu) nanoparticles and their catalysis for formic acid oxidation. Nano Lett. 2012, 12, 1102–1106.
DOI Google Scholar
14

Wang, Y.; Choi, S. I.; Zhao, X.; Xie, S. F.; Peng, H. C.; Chi, M. F.; Huang, C. Z.; Xia, Y. N. Polyol synthesis of ultrathin Pd nanowires via attachment-based growth and their enhanced activity towards formic acid oxidation. Adv. Funct. Mater. 2014, 24, 131–139.
DOI Google Scholar
15

Hu, S. Z.; Scudiero, L.; Ha, S. Electronic effect of Pd-transition metal bimetallic surfaces toward formic acid electrochemical oxidation. Electrochem. Commun. 2014, 38, 107–109.
DOI Google Scholar
16

Chen, L. Y.; Guo, H.; Fujita, T.; Hirata, A.; Zhang, W.; Inoue, A.; Chen, M. W. Nanoporous PdNi bimetallic catalyst with enhanced electrocatalytic performances for electro-oxidation and oxygen reduction reactions. Adv. Funct. Mater. 2011, 21, 4364–4370.
DOI Google Scholar
17

Zhang, Q.; Guo, X.; Liang, Z. X.; Zeng, J. H.; Yang, J.; Liao, S. J. Hybrid PdAg alloy-Au nanorods: Controlled growth, optical properties and electrochemical catalysis. Nano Res. 2013, 6, 571–580.
DOI Google Scholar
18

Zeng, J.; Zhu, C.; Tao, J.; Jin, M. S.; Zhang, H.; Li, Z. Y.; Zhu, Y. M.; Xia, Y. N. Controlling the nucleation and growth of silver on palladium nanocubes by manipulating the reaction kinetics. Angew. Chem., Int. Ed. 2012, 51, 2354–2358.
DOI Google Scholar
19

Fu, G. T.; Liu, C.; Zhang, Q.; Chen, Y.; Tang, Y. W. Polyhedral palladium–silver alloy nanocrystals as highly active and stable electrocatalysts for the formic acid oxidation reaction. Sci. Rep. 2015, 5, 13703.
DOI Google Scholar
20

Yin, Z.; Zhang, Y. N.; Chen, K.; Li, J.; Li, W. J.; Tang, P.; Zhao, H. B.; Zhu, Q. J.; Bao, X. H.; Ma, D. Monodispersed bimetallic PdAg nanoparticles with twinned structures: Formation and enhancement for the methanol oxidation. Sci. Rep. 2014, 4, 4288.
DOI Google Scholar
21

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.
DOI Google Scholar
22

Demirci, U. B. Theoretical means for searching bimetallic alloys as anode electrocatalysts for direct liquid-feed fuel cells. J. Power Sources 2007, 173, 11–18.
DOI Google Scholar
23

Bai, S.; Wang, C. M.; Deng, M. S.; Gong, M.; Bai, Y.; Jiang, J.; Xiong, Y. J. Surface polarization matters: Enhancing the hydrogen-evolution reaction by shrinking Pt shells in Pt– Pd–graphene stack structures. Angew. Chem., Int. Ed. 2014, 53, 12120–12124.
DOI Google Scholar
24

Li, B.; Long, R.; Zhong, X. L.; Bai, Y.; Zhu, Z. J.; Zhang, X.; Zhi, M.; He, J. W.; Wang, C. M.; Li, Z. -Y. et al. Investigation of size-dependent plasmonic and catalytic properties of metallic nanocrystals enabled by size control with HCl oxidative etching. Small 2012, 8, 1710–1716.
DOI Google Scholar
25

Skrabalak, S. E.; Au, L.; Li, X. D.; Xia, Y. N. Facile synthesis of Ag nanocubes and Au nanocages. Nat. Protocols 2007, 2, 2182–2190.
DOI Google Scholar
26

Chen, J. Y.; Wiley, B.; McLellan, J.; Xiong, Y. J.; Li, Z. Y.; Xia, Y. N. Optical properties of Pd-Ag and Pt-Ag nanoboxes synthesized via galvanic replacement reactions. Nano Lett. 2005, 5, 2058–2062.
DOI Google Scholar
27

Zhang, Q.; Cobley, C. M.; Zeng, J.; Wen, L. P.; Chen, J. Y.; Xia, Y. N. Dissolving Ag from Au-Ag alloy nanoboxes with H2O2: A method for both tailoring the optical properties and measuring the H2O2 concentration. J. Phys. Chem. C 2010, 114, 6396–6400.
DOI Google Scholar
28

Kresse, G.; Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 1996, 54, 11169–11186.
DOI Google Scholar
29

Bansal, V.; Li, V.; O'Mullane, A. P.; Bhargava, S. K. Shape dependent electrocatalytic behaviour of silver nanoparticles. CrystEngComm 2010, 12, 4280–4286.
DOI Google Scholar
30

Stamenkovic, V. R.; Mun, B. S.; Arenz, M.; Mayrhofer, K. J. J.; Lucas, C. A.; Wang, G. F.; Ross, P. N.; Markovic, N. M. Trends in electrocatalysis on extended and nanoscale Pt-bimetallic alloy surfaces. Nat. Mater. 2007, 6, 241–247.
DOI Google Scholar
31

Stamenkovic, V. R.; Fowler, B.; Mun, B. S.; Wang, G. F.; Ross, P. N.; Lucas, C. A.; Markovic, N. M. Improved oxygen reduction activity on Pt3Ni(111) via increased surface site availability. Science 2007, 315, 493–497.
DOI Google Scholar
32

Ji, X. L.; Lee, K. T.; Holden, R.; Zhang, L.; Zhang, J. J.; Botton, G. A.; Couillard, M.; Nazar, L. F. Nanocrystalline intermetallics on mesoporous carbon for direct formic acid fuel cell anodes. Nat. Chem. 2010, 2, 286–293.
DOI Google Scholar
33

Casado-Rivera, E.; Gál, Z.; Angelo, A. C. D.; Lind, C.; DiSalvo, F. J.; Abruña, H. D. Electrocatalytic oxidation of formic acid at an ordered intermetallic PtBi surface. ChemPhysChem 2003, 4, 193–199.
DOI Google Scholar
34

Venkateswara Rao, C.; Cabrera, C. R.; Ishikawa, Y. Graphene-supported Pt–Au alloy nanoparticles: A highly efficient anode for direct formic acid fuel cells. J. Phys. Chem. C 2011, 115, 21963–21970.
DOI Google Scholar
35

Zhao, Z. Z.; Fang, X.; Li, Y. L.; Wang, Y.; Shen, P. K.; Xie, F. Y.; Zhang, X. The origin of the high performance of tungsten carbides/carbon nanotubes supported Pt catalysts for methanol electrooxidation. Electrochem. Commun. 2009, 11, 290–293.
DOI Google Scholar
36

Arenz, M.; Stamenkovic, V.; Schmidt, T. J.; Wandelt, K.; Ross, P. N.; Markovic, N. M. The electro-oxidation of formic acid on Pt-Pd single crystal bimetallic surfaces. Phys. Chem. Chem. Phys. 2003, 5, 4242–4251.
DOI Google Scholar
37

Wang, H. F.; Liu, Z. P. Formic acid oxidation at Pt/H2O interface from periodic DFT calculations integrated with a continuum solvation model. J. Phys. Chem. C 2009, 113, 17502–17508.
DOI Google Scholar
38

Logadottir, A.; Rod, T. H.; Nørskov, J. K.; Hammer, B.; Dahl, S.; Jacobsen, C. J. H. The Brønsted–Evans–Polanyi relation and the volcano plot for ammonia synthesis over transition metal catalysts. J. Catal. 2001, 197, 229–231.
DOI Google Scholar
39

Bai, S.; Yang, L.; Wang, C. L.; Lin, Y.; Lu, J. L.; Jiang, J.; Xiong, Y. J. Boosting photocatalytic water splitting: Interfacial charge polarization in atomically controlled core–shell cocatalyst. Angew. Chem., Int. Ed. 2015, 54, 14810–14814.
DOI Google Scholar
File
nr-9-6-1590_ESM.pdf (1.9 MB)
Publication history
Copyright
Acknowledgements

Publication history

Received: 13 December 2015
Revised: 02 February 2016
Accepted: 17 February 2016
Published: 31 March 2016
Issue date: June 2016

Copyright

© Tsinghua University Press and Springer-Verlag Berlin Heidelberg 2016

Acknowledgements

Acknowledgements

This work was financially supported by the National Basic Research Program of China (No. 2014CB848900), National Natural Science Foundation of China (Nos. 21471141, 21573212, and 21473166), Anhui Provincial Natural Science Foundation (No. 1508085MB24), Recruitment Program of Global Experts, CAS Hundred Talent Program, Hefei Science Center (CAS) Funds for Users with Potential, and Fundamental Research Funds for the Central Universities (Nos. WK2060190025, WK2310000035, and WK2090050027).

Return