Corresponding Author

Qiao-xia LI(liqiaoxia@shiep.edu.cn)


Palladium is considered as an efficient anode catalyst with high catalytic activity for electrooxidation of formic acid. To further improve the catalytic activity and stability, alloying or surface modification with Sb is an effective way. In this work, the well dispersed carbon supported Pd-Sb composite nanocatalysts (Pd-Sb/C) were synthesized by traditional impregnation reduction method with trisodium citrate as the complexing agent, sodium borohydride as the reducing agent. The morphologies of Pd-Sb/C and the effects of molar ratio of Pd to Sb on the electrocatalytic properties of Pd-Sb/C for HCOOH electrooxidation were studied. The XRD and XPS analyses on the as-prepared Pd-Sb/C catalyst revealed that Sb (0) was presented on the Pd surface, and the immature alloying of Pd with Sb was achieved. Cyclic voltammetryic and chronoamperometric studies indicated a volcano-shaped relationship between Sb content and electrocatalytic activity with an optimum molar ratio of Pd:Sb=20:1. Compared with the commercial Pd/C catalyst, the Pd-Sb/C (20:1) presented the highest electrocatalytic activity and best stability. This enhancement may be attributed to the electronic effect and bi-functional effect induced by addition of Sb onto Pd surface, resulting in a weaker adsorption and accelerated oxidative removal of CO poison formed during HCOOH electrooxidation.

Graphical Abstract


palladium-based catalyst, antimony decoration, formic acid electrooxidation, impregnation reduction

Publication Date


Online Available Date


Revised Date


Received Date



[1] Yu X W, Pickup P G. Recent advances in Direct Formic Acid Fuel Cells (DFAFC)[J]. Journal of Power Sources, 2008, 182(1): 124-132.
[2] Tammam R H, Saleh M M. Electrocatalytic oxidation of formic acid on nano/micro fibers of poly(p-anisdine) modified platinum electrode[J]. Journal of Power Sources, 2014, 246: 178-183.
[3] Bertin E, Garbarino S, Guay D, et al. Electrodeposited platinum thin films with preferential (100) orientation: Characterization and electrocatalytic properties for ammonia and formic acid oxidation[J]. Journal of Power Sources, 2013, 225: 323-329.
[4] El-Nagar G A, Mohammad A M, El-Deab M S, et al. Electrocatalysis by design: Enhanced electrooxidation of formic acid at platinum nanoparticles-nickel oxide nanoparticles binary catalysts[J]. Electrochimica Acta, 2013, 94: 62-71.
[5] Waszczuk P, Barnard T M, Rice C, et al. A nanoparticle catalyst with superior activity for electrooxidation of formic acid[J]. Electrochemistry Communications, 2002, 4(7): 599-603.
[6] Rice C, Ha S, Masel R I, et al. Catalysts for direct formic acid fuel cells[J]. Journal of Power Sources, 2003, 115(2): 229-235.
[7] Zhu Y, Kang Y Y, Zou Z Q, et al. A facile preparation of carbon-supported Pd nanoparticles for electrocatalytic oxidation of formic acid[J]. Electrochemistry Communications, 2008, 10(5): 802-805.
[8] Wang J Y, Kang Y Y, Yang H, et al. Boron-doped palladium nanoparticles on carbon black as a superior catalyst for formic acid electro-oxidation[J]. The Journal of Physical Chemistry C, 2009, 113(19): 8366-8372.
[9] Lu L, Li H Z, Hong Y J, et al. Improvement of electrocatalytic performance of carbon supported Pd anodic catalyst in direct formic acid fuel cell by ethylenediamine-tetramethylene phosphonic acid[J]. Journal of Power Sources, 2012, 210: 154-157.
[10] Ren M J, Chen J, Li Y, et al. Lattice contracted Pd-hollow nanocrystals: Synthesis, structure and electrocatalysis for formic acid oxidation[J]. Journal of Power Sources, 2014, 246: 32-38.
[11] Wang J Y, Zhang H X, Jiang K, et al. From HCOOH to CO at Pd electrodes: A surface-enhanced infrared spectroscopy study[J]. Journal of the American Chemical Society, 2011, 133(38): 14876-14879.
[12] Miyake H, Okada T, Osawa G S M. Formic acid electrooxidation on Pd in acidic solutions studied by surface enhanced infrared absorption spectroscopy[J]. Physical Chemistry Chemical Physics, 2008, 10(25): 3662-3669.
[13] Yu X W, Pickup P G. Mechanistic study of the deactivation of carbon supported Pd during formic acid oxidation[J]. Electrochemistry Communications, 2009, 11(10): 2012-2014.
[14] Lee J K, Jeon H, Uhm S, et al. Influence of underpotentially deposited Sb onto Pt anode surface on the performance of direct formic acid fuel cells[J]. Electrochimica Acta, 2008, 53(21): 6089-6092.
[15] Peng B, Wang J Y, Zhang H X, et al. A versatile electroless approach to controlled modification of Sb on Pt surfaces towards efficient electrocatalysis of formic acid[J]. Electrochemistry Communications, 2009, 11(4): 831-833.
[16] Haan J L, Stafford K M, Morgan R D, et al. Performance of the direct formic acid fuel cell with electrochemically modified palladium-antimony anode catalyst[J]. Electrochimica Acta, 2010, 55(7): 2477-2481.
[17] Yu X W, Pickup P G. Deactivation resistant PdSb/C catalysts for direct formic acid fuel cells[J]. Electrochemistry Communications, 2010, 12(6): 800-803.
[18] Zhou W J, Lee J Y. Particle size effects in Pd-catalyzed electrooxidation of formic acid[J]. The Journal of Physical Chemistry C, 2008, 112(10): 3789-3793.
[19] Hu S, Scudiero L, Ha S. Electronic effect on oxidation of formic acid on supported Pd-Cu bimetallic surface[J]. Electrochimica Acta, 2012, 83: 354-358.
[20] Shen S Y, Zhao T S, Xu J B, et al. Synthesis of PdNi catalysts for the oxidation of ethanol in alkaline direct ethanol fuel cells[J]. Journal of Power Sources, 2010, 195(4): 1001-1006.
[21] Zhang J T, Qiu C C, Ma H Y, et al. Facile fabrication and unexpected electrocatalytic activity of palladium thin films with hierarchical architectures[J]. The Journal of Physical Chemistry C, 2008, 112(36): 13970-13975.



To view the content in your browser, please download Adobe Reader or, alternately,
you may Download the file to your hard drive.

NOTE: The latest versions of Adobe Reader do not support viewing PDF files within Firefox on Mac OS and if you are using a modern (Intel) Mac, there is no official plugin for viewing PDF files within the browser window.