Hierarchical nano-on-micro copper with enhanced catalytic activity towards electro-oxidation of hydrazine

Abstract

The electrochemical properties of catalyst materials are highly dependent on the materials structure and architecture. Herein, nano-on-micro Cu electrodes are fabricated by growing Cu microcrystals on Ni foam substrate, followed by introducing Cu nanocrystals onto the surface of the Cu microcrystals. The introduction of Cu nanocrystals onto the surface of Cu microcrystals is shown to dramatically increase the electrochemically active surface area and thus significantly enhances the catalytic activity of the catalyst electrode towards electro-oxidation of hydrazine. The onset potential (−1.04 V vs. Ag/AgCl) of the nano-on-micro Cu electrode is lower than those of the reported Cu-based catalysts under similar testing conditions, and a current density of 16 mA·cm⁻², which is 2 times that of the microsized Cu electrode, is achieved at a potential of −0.95 V vs. Ag/AgCl. Moreover, the nano-on-micro Cu electrode demonstrates good long-term stability.

Keywords

electrocatalysis / hydrazine oxidation / copper / nanocrystal / hierarchical architecture

References

[1] Wachsman E D, Lee K T. Lowering the temperature of solid oxide fuel cells. Science, 2011, 334(6058): 935–939

[2] Proietti E, Jaouen F, Lefèvre M, . Iron-based cathode catalyst with enhanced power density in polymer electrolyte membrane fuel cells. Nature Communications, 2011, 2: 416

[3] Serov A, Kwak C. Direct hydrazine fuel cells: A review. Applied Catalysis B: Environmental, 2010, 98(1‒2): 1–9

[4] Wang H, Ma Y, Wang R, . Liquid-liquid interface-mediated room-temperature synthesis of amorphous NiCo pompoms from ultrathin nanosheets with high catalytic activity for hydrazine oxidation. Chemical Communications, 2015, 51(17): 3570–3573

[5] Zhao X, Yin M, Ma L, . Recent advances in catalysts for direct methanol fuel cells. Energy & Environmental Science, 2011, 4(8): 2736–2753

[6] Sakamoto T, Deevanhxay P, Asazawa K, . In-situ visualization of N₂ evolution in operating direct hydrazine hydrate fuel cell by soft X-ray radiography. Journal of Power Sources, 2014, 252: 35–42

[7] Debe M K. Electrocatalyst approaches and challenges for automotive fuel cells. Nature, 2012, 486(7401): 43–51

[8] Winter M, Brodd R J. What are batteries, fuel cells, and supercapacitors? Chemical Reviews, 2004, 104(10): 4245–4270

[9] Evans G E, Kordesch K V. Hydrazine-air fuel cells. Hydrazine-air fuel cells emerge from the laboratory. Science, 1967, 158(3805): 1148–1152

[10] Rees N V, Compton R G. Carbon-free energy: a review of ammonia- and hydrazine-based electrochemical fuel cells. Energy & Environmental Science, 2011, 4(4): 1255–1260

[11] Petek M, Bruckenstein S. An isotopic labeling investigation of the mechanism of the electrooxidation of hydrazine at platinum: An electrochemical mass spectrometric study. Journal of Electroanalytical Chemistry & Interfacial Electrochemistry, 1973, 47(2): 329–333

[12] Rosca V, Koper M T. Electrocatalytic oxidation of hydrazine on platinum electrodes in alkaline solutions. Electrochimica Acta, 2008, 53(16): 5199–5205

[13] Fleischmann M, Korinek K, Pletcher D. The oxidation of hydrazine at a nickel anode in alkaline solution. Journal of Electroanalytical Chemistry & Interfacial Electrochemistry, 1972, 34(2): 499–503

[14] Fukumoto Y, Matsunaga T, Hayashi T. Electrocatalytic activities of metal electrodes in anodic oxidation of hydrazine in alkaline solution. Electrochimica Acta, 1981, 26(5): 631–636

[15] Sakamoto T, Asazawa K, Sanabria-Chinchilla J, . Combinatorial discovery of Ni-based binary and ternary catalysts for hydrazine electrooxidation for use in anion exchange membrane fuel cells. Journal of Power Sources, 2014, 247: 605–611

[16] Sanabria-Chinchilla J, Asazawa K, Sakamoto T, . Noble metal-free hydrazine fuel cell catalysts: EPOC effect in competing chemical and electrochemical reaction pathways. Journal of the American Chemical Society, 2011, 133(14): 5425–5431

[17] Jeon T Y, Watanabe M, Miyatake K. Carbon segregation-induced highly metallic Ni nanoparticles for electrocatalytic oxidation of hydrazine in alkaline media. ACS Applied Materials & Interfaces, 2014, 6(21): 18445–18449

[18] Feng G, Kuang Y, Li Y, . Three-dimensional porous superaerophobic nickel nanoflower electrodes for high-performance hydrazine oxidation. Nano Research, 2015, 8(10): 3365–3371

[19] Yan X, Liu Y, Lan J, . Crystalline–amorphous Co@CoO core–shell heterostructures for efficient electro-oxidation of hydrazine. Materials Chemistry Frontiers, 2018, 2: 96–101

[20] Liu R, Jiang X, Guo F, . Carbon fiber cloth supported micro- and nano-structured Co as the electrode for hydrazine oxidation in alkaline media. Electrochimica Acta, 2013, 94: 214–218

[21] Yang C C, Kumar A S, Kuo M C, . Copper‒palladium alloy nanoparticle plated electrodes for the electrocatalytic determination of hydrazine. Analytica Chimica Acta, 2005, 554(1‒2): 66–73

[22] Karim-Nezhad G, Jafarloo R, Dorraji P S. Copper (hydr)oxide modified copper electrode for electrocatalytic oxidation of hydrazine in alkaline media. Electrochimica Acta, 2009, 54(24): 5721–5726

[23] Gao H, Wang Y, Xiao F, . Growth of copper nanocubes on graphene paper as free-standing electrodes for direct hydrazine fuel cells. The Journal of Physical Chemistry C, 2012, 116(14): 7719–7725

[24] Jia F, Zhao J, Yu X. Nanoporous Cu film/Cu plate with superior catalytic performance toward electro-oxidation of hydrazine. Journal of Power Sources, 2013, 222: 135–139

[25] Liu C, Zhang H, Tang Y, . Controllable growth of graphene/Cu composite and its nanoarchitecture-dependent electrocatalytic activity to hydrazine oxidation. Journal of Materials Chemistry A: Materials for Energy and Sustainability, 2014, 2(13): 4580–4587

[26] Filanovsky B, Granot E, Presman I, . Long-term room-temperature hydrazine/air fuel cells based on low-cost nanotextured Cu–Ni catalysts. Journal of Power Sources, 2014, 246: 423–429

[27] Huang J, Zhao S, Chen W, . Three-dimensionally grown thorn-like Cu nanowire arrays by fully electrochemical nanoengineering for highly enhanced hydrazine oxidation. Nanoscale, 2016, 8(11): 5810–5814

[28] Lu Z, Sun M, Xu T, . Superaerophobic electrodes for direct hydrazine fuel cells. Advanced Materials, 2015, 27(14): 2361–2366

[29] Ma Y, Li H, Wang R, . Ultrathin willow-like CuO nanoflakes as an efficient catalyst for electro-oxidation of hydrazine. Journal of Power Sources, 2015, 289: 22–25

[30] Bidault F, Brett D, Middleton P, . A new application for nickel foam in alkaline fuel cells. International Journal of Hydrogen Energy, 2009, 34(16): 6799–6808

[31] Yu Y, Zhang L, Wang J, . Preparation of hollow porous Cu₂O microspheres and photocatalytic activity under visible light irradiation. Nanoscale Research Letters, 2012, 7(1): 347

[32] Elzey S, Baltrusaitis J, Bian S, . Formation of paratacamite nanomaterials via the conversion of aged and oxidized copper nanoparticles in hydrochloric acidic media. Journal of Materials Chemistry, 2011, 21(9): 3162–3169

[33] Lee Y I, Choa Y H. Adhesion enhancement of ink-jet printed conductive copper patterns on a flexible substrate. Journal of Materials Chemistry, 2012, 22(25): 12517–12522

[34] Deroubaix G, Marcus P. X-ray photoelectron spectroscopy analysis of copper and zinc oxides and sulphides. Surface and Interface Analysis, 1992, 18(1): 39–46

[35] Granot E, Filanovsky B, Presman I, . Hydrazine/air direct-liquid fuel cell based on nanostructured copper anodes. Journal of Power Sources, 2012, 204: 116–121

[36] Yan X, Tian L, Chen X. Crystalline/amorphous Ni/NiO core/shell nanosheets as highly active electrocatalysts for hydrogen evolution reaction. Journal of Power Sources, 2015, 300: 336–343

[37] Song F, Hu X. Exfoliation of layered double hydroxides for enhanced oxygen evolution catalysis. Nature Communications, 2014, 5: 4477

[38] Yan X, Tian L, Murowchick J, . Partially amorphized MnMoO₄ for highly efficient energy storage and the hydrogen evolution reaction. Journal of Materials Chemistry A: Materials for Energy and Sustainability, 2016, 4(10): 3683–3688

Acknowledgements

Z.P. acknowledges the support from the National Science Foundation (DMR1308577). X.Y. thanks the funds provided by the University of Missouri-Kansas City, School of Graduate Studies.

RIGHTS & PERMISSIONS

2018 Higher Education Press and Springer-Verlag GmbH Germany, part of Springer Nature