Journal Home > Volume 11 , Issue 9
Nano Research 2018, 11(9): 4686-4696 https://doi.org/10.1007/s12274-018-2051-7
Research Article | Issue | Published: 04 April 2018

Facile synthesis based on novel carbon-supported cyanogel of structurally ordered Pd3Fe/C as electrocatalyst for formic acid oxidation

Show Author's Information Zhenyuan Liu1,  Gengtao Fu1,2( ),  Jiahui Li1,  Zhenqi Liu1,  Lin Xu1,  Dongmei Sun1,  Yawen Tang1( )
Jiangsu Key Laboratory of New Power BatteriesJiangsu Collaborative Innovation Centre of Biomedical Functional MaterialsSchool of Chemistry and Materials ScienceNanjing Normal UniversityNanjing210023China
School of Chemical and Biomedical EngineeringNanyang Technological UniversitySingapore637459Singapore
Keywords:
formic acid oxidation, electrocatalyst, carbon@cyanogel, Pd3Fe/C, ordered intermetallic
Cite this article:
Liu Z, Fu G, Li J, et al. Facile synthesis based on novel carbon-supported cyanogel of structurally ordered Pd3Fe/C as electrocatalyst for formic acid oxidation. Nano Research, 2018, 11(9): 4686-4696. https://doi.org/10.1007/s12274-018-2051-7
Download citation
EndNote(RIS)
BibTeX

531

Views

15

Downloads

Citations

65

Crossref

N/A

WoS

65

Scopus

6

CSCD

Abstract Full text Electronic supplementary material About this article

A novel carbon-supported cyanogel (C@cyanogel)-derived strategy is used to synthesize an intermetallic Pd3Fe/C compound of the desired ordered Pd3Fe phase with a small particle size. The novelty of this work lies in using carbon-supported K2PdIICl4/K4FeII(CN)6 cyanogel as a reaction precursor, generated through the substitution of two chloride ligands by the nitrogen ends of the cyanide ligands on the metal center. The inherent nature of cyanogels can effectively suppress the movement of Pd0 and Fe0 nuclei in the crystal, benefiting the formation of the intermetallic, which is otherwise challenging via traditional synthesis techniques. The ordered Pd3Fe/C catalyst exhibits excellent catalytic activity and good cycle stability for the formic acid oxidation (FAO) reaction relative to the properties of disordered Pd3Fe/C and commercial Pd/C catalysts, demonstrating that the ordered Pd3Fe/C is a promising replacement for commercial Pd-based catalysts. The outstanding performance can be ascribed to the full isolation of active sites in the ordered Pd3Fe structure and the modified electronic structure of the active components. This work provides an effective and novel route to obtain Pd-based intermetallic compounds with potential applications in a wide range of electrocatalysis.


menu
Abstract
Full text
Outline
Electronic supplementary material
About this article

Facile synthesis based on novel carbon-supported cyanogel of structurally ordered Pd3Fe/C as electrocatalyst for formic acid oxidation

Show Author's information Zhenyuan Liu1, Gengtao Fu1,2( ), Jiahui Li1, Zhenqi Liu1, Lin Xu1, Dongmei Sun1, Yawen Tang1( )
Jiangsu Key Laboratory of New Power BatteriesJiangsu Collaborative Innovation Centre of Biomedical Functional MaterialsSchool of Chemistry and Materials ScienceNanjing Normal UniversityNanjing210023China
School of Chemical and Biomedical EngineeringNanyang Technological UniversitySingapore637459Singapore

Abstract

A novel carbon-supported cyanogel (C@cyanogel)-derived strategy is used to synthesize an intermetallic Pd3Fe/C compound of the desired ordered Pd3Fe phase with a small particle size. The novelty of this work lies in using carbon-supported K2PdIICl4/K4FeII(CN)6 cyanogel as a reaction precursor, generated through the substitution of two chloride ligands by the nitrogen ends of the cyanide ligands on the metal center. The inherent nature of cyanogels can effectively suppress the movement of Pd0 and Fe0 nuclei in the crystal, benefiting the formation of the intermetallic, which is otherwise challenging via traditional synthesis techniques. The ordered Pd3Fe/C catalyst exhibits excellent catalytic activity and good cycle stability for the formic acid oxidation (FAO) reaction relative to the properties of disordered Pd3Fe/C and commercial Pd/C catalysts, demonstrating that the ordered Pd3Fe/C is a promising replacement for commercial Pd-based catalysts. The outstanding performance can be ascribed to the full isolation of active sites in the ordered Pd3Fe structure and the modified electronic structure of the active components. This work provides an effective and novel route to obtain Pd-based intermetallic compounds with potential applications in a wide range of electrocatalysis.

Keywords: formic acid oxidation, electrocatalyst, carbon@cyanogel, Pd3Fe/C, ordered intermetallic

References(50)

1

Liu, M. M.; Zhang, R. Z.; Chen, W. Graphene-supported nanoelectrocatalysts for fuel cells: Synthesis, properties, and applications. Chem. Rev. 2014, 114, 5117–5160.
DOI Google Scholar
2

Peng, Z. M.; Yang, H. PtAu bimetallic heteronanostructures made by post-synthesis modification of Pt-on-Au nanoparticles. Nano Res. 2009, 2, 406–415.
DOI Google Scholar
3

Klinkova, A.; De Luna, P.; Sargent, E. H.; Kumacheva, E.; Cherepanov, P. V. Enhanced electrocatalytic performance of palladium nanoparticles with high energy surfaces in formic acid oxidation. J. Mater. Chem. A 2017, 5, 11582–11585.
DOI Google Scholar
4

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
5

Xu, H.; Ding, L. X.; Feng, J. X.; Li, G. R. Pt/Ni(OH)2- NiOOH/Pd multi-walled hollow nanorod arrays as superior electrocatalysts for formic acid electrooxidation. Chem. Sci. 2015, 6, 6991–6998.
DOI Google Scholar
6

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.
DOI Google Scholar
7

Jiang, X.; Fu, G. T.; Wu, X.; Liu, Y.; Zhang, M. Y.; Sun, D. M.; Xu, L.; Tang, Y. W. Ultrathin AgPt alloy nanowires as a high-performance electrocatalyst for formic acid oxidation. Nano Res. 2018, 11, 499–510.
DOI Google Scholar
8

Luan, C. L.; Zhou, Q. X.; Wang, Y.; Xiao, Y.; Dai, X. P.; Huang, X. L.; Zhang, X. A general strategy assisted with dual reductants and dual protecting agents for preparing Pt-based alloys with high-index facets and excellent electrocatalytic performance. Small 2017, 13, 1702617.
DOI Google Scholar
9

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.
DOI Google Scholar
10

Ho, S. F.; Mendoza-Garcia, A.; Guo, S. J.; He, K.; Su, D.; Liu, S.; Metin, Ö.; Sun, S. H. A facile route to monodisperse MPd (M = Co or Cu) alloy nanoparticles and their catalysis for electrooxidation of formic acid. Nanoscale 2014, 6, 6970–6973.
DOI Google Scholar
11

Yu, X. W.; Pickup, P. G. Recent advances in direct formic acid fuel cells (DFAFC). J. Power Sources 2008, 182, 124–132.
DOI Google Scholar
12

Mahmood, A.; Saleem, F.; Lin, H. F.; Ni, B.; Wang, X. Crystallinity-induced shape evolution of Pt-Ag nanosheets from branched nanocrystals. Chem. Commun. 2016, 52, 10547–10550.
DOI Google Scholar
13

Qin, Y. C.; Zhang, X.; Dai, X. P.; Sun, H.; Yang, Y.; Li, X. S.; Shi, Q. X.; Gao, D. W.; Wang, H.; Yu, N. F. et al. Graphene oxide-assisted synthesis of Pt-Co alloy nanocrystals with high-index facets and enhanced electrocatalytic properties. Small 2016, 12, 524–533.
DOI Google Scholar
14

Wang, X. X.; Yang, J. D.; Yin, H. J.; Song, R.; Tang, Z. Y. "Raisin bun"-like nanocomposites of palladium clusters and porphyrin for superior formic acid oxidation. Adv. Mater. 2013, 25, 2728–2732.
DOI Google Scholar
15

Sun, H. Y.; Guo, X.; Ye, W.; Kou, S. F.; Yang, J. Charge transfer accelerates galvanic replacement for PtAgAu nanotubes with enhanced catalytic activity. Nano Res. 2016, 9, 1173–1181.
DOI Google Scholar
16

Ha, S.; Larsen, R.; Masel, R. I. Performance characterization of Pd/C nanocatalyst for direct formic acid fuel cells. J. Power Sources 2005, 144, 28–34.
DOI Google Scholar
17

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
18

Huang, X. Q.; Tang, S. H.; Mu, X. L.; Dai, Y.; Chen, G. X.; Zhou, Z. Y.; Ruan, F. X.; Yang, Z. L.; Zheng, N. F. Freestanding palladium nanosheets with plasmonic and catalytic properties. Nat. Nanotechnol. 2011, 6, 28–32.
DOI Google Scholar
19

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
20

Jiang, K.; Zhang, H. X.; Zou, S. Z.; Cai, W. B. Electrocatalysis of formic acid on palladium and platinum surfaces: From fundamental mechanisms to fuel cell applications. Phys. Chem. Chem. Phys. 2014, 16, 20360–20376.
DOI Google Scholar
21

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
22
Yan, X. X.; Hu, X. J.; Fu, G. T.; Xu, L.; Lee, J. M.; Tang, Y. W. Facile synthesis of porous Pd3Pt half-shells with rich " active sites" as efficient catalysts for formic acid oxidation. Small, in press, DOI: 10.1002/smll.201703940.https://doi.org/10.1002/smll.201703940
DOI
23

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.
DOI Google Scholar
24

Matin, M. A.; Jang, J. H.; Kwon, Y. U. PdM nanoparticles (M = Ni, Co, Fe, Mn) with high activity and stability in formic acid oxidation synthesized by sonochemical reactions. J. Power Sources 2014, 262, 356–363.
DOI Google Scholar
25

Du, C. Y.; Chen, M.; Wang, W. G.; Yin, G. P.; Shi, P. F. Electrodeposited PdNi2 alloy with novelly enhanced catalytic activity for electrooxidation of formic acid. Electrochem. Commun. 2010, 12, 843–846.
DOI Google Scholar
26

Lu, Q. Q.; Wang, H. J.; Eid, K.; Alothman, Z. A.; Malgras, V.; Yamauchi, Y.; Wang, L. Synthesis of hollow platinum-palladium nanospheres with a dendritic shell as efficient electrocatalysts for methanol oxidation. Chem. Asian J. 2016, 11, 1939–1944.
DOI Google Scholar
27

Chen, D.; Sun, P. C.; Liu, H.; Yang, J. Bimetallic Cu-Pd alloy multipods and their highly electrocatalytic performance for formic acid oxidation and oxygen reduction. J. Mater. Chem. A 2017, 5, 4421–4429.
DOI Google Scholar
28

Saleem, F.; Ni, B.; Yong, Y.; Gu, L.; Wang, X. Ultra-small tetrametallic Pt-Pd-Rh-Ag nanoframes with tunable behavior for direct formic acid/methanol oxidation. Small 2016, 12, 5261–5268.
DOI Google Scholar
29

Mao, J. J.; Liu, Y. X.; Chen, Z.; Wang, D. S.; Li, Y. D. Bimetallic Pd-Cu nanocrystals and their tunable catalytic properties. Chem. Commun. 2014, 50, 4588–4591.
DOI Google Scholar
30

McMillan, R. A.; Howard, J.; Zaluzec, N. J.; Kagawa, H. K.; Mogul, R.; Li, Y. F.; Paavola, C. D.; Trent, J. D. A self-assembling protein template for constrained synthesis and patterning of nanoparticle arrays. J. Am. Chem. Soc. 2005, 127, 2800–2801.
DOI Google Scholar
31

Chai, J.; Li, F. H.; Hu, Y. W.; Zhang, Q. X.; Han, D. X.; Niu, L. Hollow flower-like aupd alloy nanoparticles: One step synthesis, self-assembly on ionic liquid-functionalized graphene, and electrooxidation of formic acid. J. Mater. Chem. 2011, 21, 17922–17929.
DOI Google Scholar
32

Tominaka, S.; Momma, T.; Osaka, T. Electrodeposited Pd-Co catalyst for direct methanol fuel cell electrodes: Preparation and characterization. Electrochim. Acta 2008, 53, 4679–4686.
DOI Google Scholar
33

Zhang, Z. H.; Zhang, C.; Sun, J. Z.; Kou, T. Y.; Zhao, C. C. Ultrafine nanoporous Cu-Pd alloys with superior catalytic activities towards electro-oxidation of methanol and ethanol in alkaline media. RSC Adv. 2012, 2, 11820–11828.
DOI Google Scholar
34

Rong, H. P.; Mao, J. J.; Xin, P. Y.; He, D. S.; Chen, Y. J.; Wang, D. S.; Niu, Z. Q.; Wu, Y.; Li, Y. D. Kinetically controlling surface structure to construct defect-rich intermetallic nanocrystals: Effective and stable catalysts. Adv. Mater. 2016, 28, 2540–2546.
DOI Google Scholar
35

Liu, Y. X.; Liu, X. W.; Feng, Q. C.; He, D. S.; Zhang, L. B.; Lian, C.; Shen, R.; Zhao, G. F.; Ji, Y. J.; Wang, D. S. et al. Intermetallic NixMy (M = Ga and Sn) nanocrystals: A non-precious metal catalyst for semi-hydrogenation of alkynes. Adv. Mater. 2016, 28, 4747–4754.
DOI Google Scholar
36

Cui, Z. M.; Chen, H.; Zhao, M. T.; DiSalvo, F. J. High-performance Pd3Pb intermetallic catalyst for electrochemical oxygen reduction. Nano Lett. 2016, 16, 2560–2566.
DOI Google Scholar
37

Shi, Q. R.; Zhu, C. Z.; Bi, C. X.; Xia, H. B.; Engelhard, M. H.; Du, D.; Lin, Y. H. Intermetallic Pd3Pb nanowire networks boost ethanol oxidation and oxygen reduction reactions with significantly improved methanol tolerance. J. Mater. Chem. A 2017, 5, 23952–23959.
DOI Google Scholar
38

Du, X. X.; He, Y.; Wang, X. X.; Wang, J. N. Fine-grained and fully ordered intermetallic PtFe catalysts with largely enhanced catalytic activity and durability. Energy Environ. Sci. 2016, 9, 2623–2632.
DOI Google Scholar
39

Gunji, T.; Noh, S. H.; Tanabe, T.; Han, B.; Nien, C. Y.; Ohsaka, T.; Matsumoto, F. Enhanced electrocatalytic activity of carbon-supported ordered intermetallic palladium-lead (Pd3Pb) nanoparticles toward electrooxidation of formic acid. Chem. Mater. 2017, 29, 2906–2913.
DOI Google Scholar
40

Li, X.; An, L.; Wang, X. Y.; Li, F.; Zou, R. Q.; Xia, D. G. Supported sub-5nm Pt-Fe intermetallic compounds for electrocatalytic application. J. Mater. Chem. 2012, 22, 6047–6052.
DOI Google Scholar
41

Cui, Z. M.; Li, L. J.; Manthiram, A.; Goodenough, J. B. Enhanced cycling stability of hybrid Li-air batteries enabled by ordered Pd3Fe intermetallic electrocatalyst. J. Am. Chem. Soc. 2015, 137, 7278–7281.
DOI Google Scholar
42

Kuttiyiel, K. A.; Sasaki, K.; Su, D.; Wu, L. J.; Zhu, Y. M.; Adzic, R. R. Gold-promoted structurally ordered intermetallic palladium cobalt nanoparticles for the oxygen reduction reaction. Nat. Commun. 2014, 5, 5185.
DOI Google Scholar
43

Zhang, G. J.; Zhang, L.; Shen, L. P.; Chen, Y.; Zhou, Y. M.; Tang, Y. W.; Lu, T. H. Synthesis and electrocatalytic properties of palladium network nanostructures. ChemPlusChem 2012, 77, 936–940.
DOI Google Scholar
44

Liu, H. M.; Li, J. H.; Wang, L. J.; Tang, Y. W.; Xia, B. Y.; Chen, Y. Trimetallic PtRhNi alloy nanoassemblies as highly active electrocatalyst for ethanol electrooxidation. Nano Res. 2017, 10, 3324–3332.
DOI Google Scholar
45

Fu, G. T.; Liu, Z. Y.; Zhang, J. F.; Wu, J. Y.; Xu, L.; Sun, D. M.; Zhang, J. B.; Tang, Y. W.; Chen, P. Spinel MnCo2O4 nanoparticles cross-linked with two-dimensional porous carbon nanosheets as a high-efficiency oxygen reduction electrocatalyst. Nano Res. 2016, 9, 2110–2122.
DOI Google Scholar
46

Fu, G. T.; Liu, H. M.; You, N. K.; Wu, J. Y.; Sun, D. M.; Xu, L.; Tang, Y. W.; Chen, Y. Dendritic platinum-copper bimetallic nanoassemblies with tunable composition and structure: Arginine- driven self-assembly and enhanced electrocatalytic activity. Nano Res. 2016, 9, 755–765.
DOI Google Scholar
47

Hammer, B.; Morikawa, Y.; Nørskov, J. K. CO chemisorption at metal surfaces and overlayers. Phys. Rev. Lett. 1996, 76, 2141– 2144.
DOI Google Scholar
48

Wang, Y. C.; Chen, J. W.; Zhou, F. L.; Zhang, J.; Wei, X. Y.; Luo, R.; Wang, G.; Wang, R. L. Dealloyed platinum-copper with isolated Pt atom surface: Facile synthesis and promoted dehydrogenation pathway of formic acid electro-oxidation. J. Electroanal. Chem. 2017, 799, 78–83.
DOI Google Scholar
49

Kristian, N.; Yan, Y. S.; Wang, X. Highly efficient submonolayer Pt-decorated Au nano-catalysts for formic acid oxidation. Chem. Commun. 2008, 353–355.
DOI Google Scholar
50

Cui, Z. M.; Chen, H.; Zhou, W. D.; Zhao, M. T.; DiSalvo, F. J. Structurally ordered Pt3Cr as oxygen reduction electrocatalyst: Ordering control and origin of enhanced stability. Chem. Mater. 2015, 27, 7538–7545.
DOI Google Scholar
File
12274_2018_2051_MOESM1_ESM.pdf (1,001.6 KB)
Publication history
Copyright
Acknowledgements

Publication history

Received: 31 January 2018
Revised: 16 February 2018
Accepted: 12 March 2018
Published: 04 April 2018
Issue date: September 2018

Copyright

© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2018

Acknowledgements

Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (Nos. 21503111, 21576139, and 21376122), Natural Science Foundation of Jiangsu Province (No. BK20171473), Natural Science Foundation of Jiangsu Higher Education Institutions of China (No. 16KJB150020) and Key Laboratory of Renewable Energy, Chinese Academy of Sciences (No. Y607k51001). The authors are also grateful for the supports from National and Local Joint Engineering Research Center of Biomedical Functional Materials and a project sponsored by the Priority Academic Program Development of Jiangsu Higher Education Institutions.

Return