Abstract
Effects of adding varied amounts of copper to carbon-supported nickel particles on their structure, composition and electrocatalytic activity for the hydrogen oxidation and evolution reactions in alkaline medium have been explored. Ni1-x Cu x /C catalysts were prepared by the incipient wetness impregnation. Comprehensive characterization of the catalysts included X-ray powder diffraction, X-ray photoelectron spectroscopic, transmission electron microscopic and cyclic voltammetric analyses, while atomistic Monte Carlo simulations have been undertaken to obtain further insights into the structure of the bimetallic NiCu nanoparticles. We found that compared to monometallic Ni, NiCu nanoparticles show lower propensity towards oxidation under ambient conditions. Furthermore, we report that adding Cu allows increasing the surface-weighted electrocatalytic activity, and the specific surface area of Ni1-x Cu x /C electrodes, both contributing to a ca four-fold enhancement of the mass-weighted activity. The nature of the synergistic interactions between Ni and Cu is proposed on the basis of the analysis of experimental data and Monte Carlo structural modelling results.
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Wang Y-J, Qiao J, Baker R, Zhang J (2013) Alkaline polymer electrolyte membranes for fuel cell applications. Chem Soc Rev 42:5768–5787
Varcoe JR, Atanassov P, Dekel DR, Herring AM, Hickner MA, Kohl PA, Kucernak AR, Mustain WE, Nijmeijer K, Scott K, Xu T, Zhuang L (2014) Anion-exchange membranes in electrochemical energy systems. Energy Environ Sci 7:3135–3191
Durst J, Siebel A, Simon C, Hasché F, Herranz J, Gasteiger HA (2014) New insights into the electrochemical hydrogen oxidation and evolution reaction mechanism. Energy Environ Sci 7:2255–2260
Sheng W, Myint M, Chen JG, Yan Y (2013) Correlating the hydrogen evolution reaction activity in alkaline electrolytes with the hydrogen binding energy on monometallic surfaces. Energy Environ Sci 6:1509–1512
Marini S, Salvi P, Nelli P, Pesenti R, Villa M, Kiros Y (2013) Stable and inexpensive electrodes for the hydrogen evolution reaction. Int J Hydrog Energy 38:11484–11495
Solmaz R, Döner A, Kardaş G (2008) Electrochemical deposition and characterization of NiCu coatings as cathode materials for hydrogen evolution reaction. Electrochem Commun 10:1909–1911
Ngamlerdpokin K, Tantavichet N (2014) Electrodeposition of nickel–copper alloys to use as a cathode for hydrogen evolution in an alkaline media. Int J Hydrog Energy 39:2505–2515
Ahn SH, Park HH-Y, Choi I, Yoo SJ, Hwang SJ, Kim H-J, Cho EA, Yoon CW, Son H, Hernandez JM, Nam SW, Lim T-H, Kim S-K, Jang JH (2013) Electrochemically fabricated NiCu alloy catalysts for hydrogen production in alkaline water electrolysis. Int J Hydrog Energy 38:13493–13501
Sheng W, Bivens AP, Myint M, Zhuang Z, Forest RV, Fang Q, Chen JG, Yan Y (2014) Non-precious metal electrocatalysts with high activity for hydrogen oxidation reaction in alkaline electrolytes. Energy Environ Sci 7:1719–1724
Kiros Y, Majari M, Nissinen TA (2003) Effect and characterization of dopants to Raney nickel for hydrogen oxidation. J Alloy Compd 360:279–285
Conway BE, Bockris JO (1957) Electrolytic Hydrogen Evolution Kinetics and Its Relation to the Electronic and Adsorptive Properties of the Metal. J Chem Phys 26:532–541
Trasatti S (1972) Work function, electronegativity, and electrochemical behaviour of metals iii. Electrolytic hydrogen evolution in acid solutions. J Electroanal Chem 39:163–184
Parsons R (1958) The rate of electrolytic hydrogen evolution and the heat of adsorption of hydrogen. Trans Faraday Soc 54:1053–1063
Greeley J, Jaramillo TF, Bonde J, Chorkendorff IB, Nørskov JK (2006) Computational high-throughput screening of electrocatalytic materials for hydrogen evolution. Nat Mater 5:909–913
Petrii OA, Tsirlina GA (1994) Electrocatalytic activity prediction for hydrogen electrode reaction: intuition, art, science. Electrochim Acta 39:1739–1747
Quaino P, Juarez F, Santos E, Schmickler W (2014) Volcano plots in hydrogen electrocatalysis—uses and abuses. Beilstein J Nanotechnol 5:846–854
Santos E, Hindelang P, Quaino P, Schulz EN, Soldano G, Schmickler W (2011) Hydrogen electrocatalysis on single crystals and on nanostructured electrodes. ChemPhysChem 12:2274–2279
Santos E, Quaino P, Hindelang PF, Schmickler W (2010) Hydrogen evolution on a pseudomorphic Cu-layer on Ni(111)—A theoretical study. J Electroanal Chem 649:149–152
Watanabe K, Hashiba M, Yamashina T (1976) A quantitative analysis of surface segregation and in-depth profile of copper-nickel alloys. Surf Sci 61:483–490
Ling DT, Miller JN, Lindau I, Spicer WE, Stefan PM (1978) Oscillations in the compositional depth profile of Cu/Ni alloys: a study by UPS. Surf Sci 74:612–620
Brongersma HH, Buck TM (1975) Selected topics in low-energy ion scattering: surface segregation in Cu/Ni alloys and ion neutralization. Surf Sci 53:649–658
Tsong TT, Ng YS, McLane SB (1980) Surface segregation of Ni-Cu alloy in nitrogen and oxygen: an atom-probe field-ion microscope study. J Appl Phys 51:6189–6191
Sakurai T, Hashizume T, Kobayashi A, Sakai A, Hyodo S, Kuk Y, Pickering HW (1986) Surface segregation of Ni-Cu binary alloys studied by an atom-probe. Phys Rev B 34:8379–8390
Donnelly RG, King TS (1978) Surface composition and surface cluster size distribution of Cu-Ni alloys via a monte carlo method. Surf Sci 74:89–108
Foiles SM (1985) Calculation of the surface segregation of Ni-Cu alloys with the use of the embedded-atom method. Phys Rev B 32:7685–7693
Yan XL, Wang JY (2013) Size effects on surface segregation in Ni–Cu alloy thin films. Thin Solid Films 529:483–487
Xie Y-P, Zhao S-J (2011) The energetic and structural properties of bcc NiCu, FeCu alloys: a first-principles study. Comput Mater Sci 50:2586–2591
Wang HY, Najafabadi R, Srolovitz DJ, LeSar R (1992) (100) surface segregation in Cu-Ni alloys. Phys Rev B 45:12028–12042
Huang S, Balbuena PB (2002) Melting of bimetallic Cu–Ni nanoclusters. J Phys Chem B 106:7225–7236
Mainardi DS, Balbuena PB (2001) Monte Carlo simulation of Cu–Ni nanoclusters: surface segregation studies. Langmuir 17:2047–2050
Oshchepkov AG, Simonov AN, Simonov PA, Shmakov AN, Rudina NA, Ishchenko AV, Cherstiouk OV, Parmon VN (2014) Interrelation between catalytic activity for oxygen electroreduction and structure of supported platinum. J Electroanal Chem 729:34–42
Machado SAS, Avaca LA (1994) The hydrogen evolution reaction on nickel surfaces stabilized by H-absorption. Electrochim Acta 39:1385–1391
Sarkany J (1982) On the use of the dynamic pulse method to measure metal surface areas. J Catal 76:75–83
UK Surface Analysis Forum. http://www.uksaf.org/xpspeak41.zip
Hall DS, Bock C, MacDougall BR (2013) The Electrochemistry of Metallic Nickel: oxides, Hydroxides, Hydrides and Alkaline Hydrogen Evolution. J Electrochem Soc 160:F235–F243
Medway SL, Lucas CA, Kowal A, Nichols RJ, Johnson D (2006) In situ studies of the oxidation of nickel electrodes in alkaline solution. J Electroanal Chem 587:172–181
Domnick R, Held G, Witte P, Steinrück H-P (2001) The transition from oxygen chemisorption to oxidation of ultra-thin Ni layers on Cu(111). J Chem Phys 115:1902–1908
Holloway PH (1981) Chemisorption and oxide formation on metals: oxygen–nickel reaction. J Vac Sci Technol 18:653–659
Acknowledgments
The authors acknowledge financial support from the grant ERA.Net RUS No. 208 and Russian Academy of Science (Project No. V.46.4.4). Clarifying discussions with Prof Wolfgang Schmickler and Prof. Elizabeth Santos (Ulm University, Germany) are highly appreciated. A.G.O. acknowledges financial support from Russian UMNIK Program No. 10U/01-13 and PhD Eiffel scholarship of French government. T.Y.K acknowledges financial support from the Skolkovo Foundation (Grant Agreement for Russian educational organizations No. 3 of 25.12.2014). R.R.N and D.V.G. thank the Russian Foundation for Basic Research (Project No. 14-03-00935a).
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Oshchepkov, A.G., Simonov, P.A., Cherstiouk, O.V. et al. On the Effect of Cu on the Activity of Carbon Supported Ni Nanoparticles for Hydrogen Electrode Reactions in Alkaline Medium. Top Catal 58, 1181–1192 (2015). https://doi.org/10.1007/s11244-015-0487-5
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DOI: https://doi.org/10.1007/s11244-015-0487-5