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DOI: 10.1002/celc.201300172

Fabrication of Nanoporous Nickel Coatings by Template-

Assisted Electrodeposition
Adam Slabon,*[a, b] Frank Krumeich,[a] Florian Wchter,[a] and Reinhard Nesper[a]
Porous metals have recently received increased attention as 30 g L 1 boric acid (Scheme 1, step b). A porous structure was
catalysts, filters, as well as lightweight and composite materi- induced by electrochemical etching of copper from the nickel–
als.[1] Moreover, they can also be used as electrodes,[1b] and copper layer (Scheme 1, step c).[9] The template was finally re-
special attention has been focused on preparation techniques moved by dissolution, leaving a replica in the arrangement of
for porous gold electrodes.[2] However, two challenges remain a thin film (Scheme 1, step d).
in the synthesis of porous metals: 1) the precise control of
morphology and 2) achievement of pore sizes in the submi-
cron range.[3] Until now, it has not been possible to gain pre-
cise control over pore size and pore-size distribution within
the metal coating, unlike in mesoporous silicates, which dis-
play interior channels of exactly defined dimensions on the
nanometer scale.[4]
Electroplating of nickel and nickel-based alloys has been
used since the beginning of the 20th century, and the interest
in such metal films has mainly been driven by its technological
application as surface coatings.[5] For example, nickel–copper
alloys, such as the nickel-rich “monel” (ca. 70 % Ni), exhibit ex-
traordinary corrosion resistivity.[6] Electrodeposition offers the Scheme 1. Procedure for the fabrication of porous nickel thin-films. a) Depo-
possibility to modulate the nickel-to-copper ratio by choosing sition of the template (i.e. polystyrene nanospheres), b) potentiostatic co-
deposition of nickel and copper on the template, c) electrochemical etching
appropriate conditions such as applied voltage and/or current
of copper, and d) template removal through dissolution in acetone.
density, pulsed or potentio-/galvanostatic techniques, chemical
additives, complexing agents, and concentration of the cations Figure 1 shows the cyclic voltammogram for the experimen-
in the metallic bath.[7] Furthermore, pulsed techniques have tal setup. When applying a cathodic current, copper (II) is re-
emerged as powerful tools for creating nickel nanoparticles, duced to copper (I) at a potential (E) of E = 0.1 V, prior to the
with remarkable control over the grain size.[8] Electrochemical reduction reactions of nickel (II). For more negative values of E,
dealloying of copper in sulfamate solution from homogenous the amount of nickel increases in the co-deposited matrix.
single-phase Ni1 xCux alloys has been reported to yield a submi- Consequently, we applied a constant voltage of E = 1.5 V for
cron porous structure of the remaining deposit consisting of the deposition of nickel and copper, to achieve a sufficient
nickel.[9] Although many mechanistic[6, 10] and kinetic studies[11] amount of nickel. Copper is electrochemically etched from the
have been devoted towards electrodeposition of nickel and deposit at potentials higher than E = + 1.1 V; therefore, in our
copper, there is a relatively small amount of reports on precise
control of the thin-film morphology.[2a] In this work, we present
a method to fabricate nanoporous nickel thin-films, which can
be produced either as spheres or nanotubes.
The synthetic procedure is shown in Scheme 1. Spherical
polystyrene nanoparticles were chosen as a template and de-
posited on the working electrode (Scheme 1, step a). Chro-
noamperometric electrodeposition was performed at pH
values ranging from 3 to 3.5 for 40 min in a metallic bath con-
sisting of 403.0 g L 1 NiSO4·6 H2O, 9.0 g L 1 CuSO4·5 H2O and

[a] Dr. A. Slabon, Dr. F. Krumeich, Dr. F. Wchter, Prof. Dr. R. Nesper
Department of Chemistry, ETH Zurich
Wolfgang-Pauli-Str. 10, CH-8093 Zurich (Switzerland)
[b] Dr. A. Slabon
Department of Chemistry, University of California, Berkeley
Hildebrand Hall BG6, Berkeley, CA 94720 (USA) Figure 1. Cyclic voltammogram for the metallic bath, consisting of 1.53 m
E-mail: aslabon@berkeley.edu NiSO4, 0.04 m CuSO4, and 0.49 m B(OH)3, at a scan rate of v = 100 mV s 1.[12]
Supporting Information for this article is available on the WWW under The voltage range was set from 1.5 V to +1.5 V. All voltages are reported
http://dx.doi.org/10.1002/celc.201300172. versus a saturated Ag/AgCl electrode.

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Figure 3. SEM images of nickel thin-films, indicating a morphology related

to hollow sphere arrangements. The nanostructures were obtained after
washing in acetone and subsequent electrochemical etching of copper from
Figure 2. Comparison of experimental powder XRD patterns of deposited the deposit. Figure 3 d represents a higher magnification of Figure 3 c.
nickel–copper films and porous nickel thin-films, as well as the theoretical
patterns of elemental nickel and copper. The co-deposited thin-films reveal
a significantly higher amount of copper than nickel. The XRD patterns were mined, to a certain extent, by the nickel-to-copper ratio, and
recorded on samples scratched from the working electrode.
smaller pore sizes can be achieved for co-deposits with higher
nickel contents. As the composition is a function of the applied
experiments, we used a potential of E = + 1.4 V in order to voltage,[9, 12] smaller pores are expected by applying more neg-
remove all copper from the Ni–Cu deposit. ative potentials.
Powder X-Ray diffraction (XRD) experiments were carried out In order to investigate whether this method would be also
to determine whether the deposited film represents a single- applicable for the synthesis of porous nanotubes, we per-
phase nickel–copper alloy or a heterogeneous deposit of ele- formed experiments with the same protocol with porous ano-
mental nickel and copper (Figure 2). Both elements crystallize dized alumina oxide (AAO) as the template. The morphology
with a face-centered cubic (fcc) structure and the nickel– of the nickel deposit, after copper etching and AAO dissolu-
copper alloys Ni1 xCux (0 < x < 1) display a full homogeneity tion, is presented in Figure 4. The electrodeposited nanostruc-
range in which both types of atoms are statistically distributed tures of nickel appear as hierarchically ordered nanotubes,
on the crystallographic sites. Depending on the composition, which are highly orientated perpendicular to the surface of the
the lattice parameters should, therefore, be between those of substrate. The lengths of these nanotubes are approximately
elemental nickel and copper, respectively. The experimental 2.0 mm. As expected for a replica of porous AAO, the nano-
powder XRD patterns of the co-deposited and electrochemical- tubes display a width of 200 nm. A peculiar feature of the
ly etched films are compared in Figure 2, together with the cal- nanostructures is their porous wall structure, containing meso-
culated values of copper and nickel. The sharp reflection peaks pores as well as macropores. Although the degree of porosity
indicate good crystallinity of the electrodeposited films. The
XRD reflections match to elemental nickel and copper; there-
fore, no alloy formation is found to occur during electrodeposi-
tion at E = 1.5 V (Figure 1).During this process, the copper
and nickel cations are reduced and create a metallic coating
around the polystyrene nanoparticles. Powder XRD patterns,
recorded after electrochemical etching, reveal only reflections
of elemental nickel and, thus, prove that copper was complete-
ly removed from the metallic deposit.
Figure 3 presents the scanning electron microscopy (SEM)
images of the deposited nickel nanostructures. After nickel–
copper co-deposition, in which the template is coated with the
metal, and subsequent dealloying, a thin film of porous nickel
is obtained. The metal resembles a replica of the spherical
polystyrene template. After electrochemical etching of copper
from the nickel–copper matrix and dissolution of the template,
a uniform residue of a hollow sphere ensemble remains. The
Figure 4. SEM images of porous nickel nanotubes. The nanotubes remained
thin films display not only macropores, but also mesopores strongly attached to the gold layer, which was sputtered on the surface of
with sizes of approximately 50 nm. The pore size is deter- the AAO template.

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is high (Figure 3 c), the morphology still resembles distinctive
nanotubes. The porous structure of the nanotubes is apparent
over their entire length, as can be seen in Figure 3 d. Copper
can only be removed from the nickel–copper matrix in one di-
rection, because the other side is blocked by the sputtered
gold layer. Electrochemical etching of copper can, therefore,
be regarded as a sufficient method to ensure the porosity of
nickel inside the AAO template. Energy-dispersive X-ray (EDX)
analysis confirms nickel as the only metallic constituent of the
porous nanotubes (see the Supporting Information), which is
consistent with the results of the powder XRD experiments.
In summary, we have demonstrated the precise control over
the morphology and porosity of nickel thin-films on the nano-
scale. Porous nickel nanostructures in the form of hollow
spheres and tubes were synthesized by using electrochemical
co-deposition of nickel and copper and subsequent electro-
chemical etching. Although the templates used were not
suited for the fabrication of porous materials, the porosity
could be induced by electrochemical removal of copper. SEM
images revealed that the porous structure of nickel was pres-
ent over the entire template surface. These hierarchically or-
dered nanostructures have potential applications as building
blocks for electrochemical devices, such as current collectors in
energy-storage systems.[13]
Experimental Section
Spherical polystyrene nanoparticles were synthesized by carefully
dissolving commercial polystyrene in acetone (100 mL). In case of
the appearance of an oleic suspension, the reaction mixture
should be filtered to gain a clear solution. The mixture was subse-
quently stirred vigorously and precipitated by quickly pouring an
equivalent amount of distilled water into the reaction mixture. A
suspension of spherical polystyrene nanoparticles in water was ob-
tained by evaporating the acetone at 60 8C. The suspension was fil-
tered over a polyethersulfone (PES) membrane with a pore size of
220 nm (TPP, Switzerland) in order to get a polymeric template
with particles in the nanosize region. The polystyrene suspension
was ultrasonicated for 10 min and dropped over an area of 3.5 cm2
onto a 2.2 mm-thick sodalime glass (TCO22–7 Solaronix, Switzer-
land), which was coated on one side with a fluorine-doped tin
oxide (FTO) layer. The water was left to evaporate, yielding a film
of spherical polystyrene particles on the FTO–glass (see Figure S5
in the Supporting Information). The working electrode was used as
the template for the fabrication of a nickel–copper deposit. Chro-
noamperometric electrodeposition was performed at pH values
ranging from 3 to 3.5 for 40 min in a metallic bath consisting of
NiSO4·6 H2O (403.0 g L 1, 99 % Sigma Aldrich), CuSO4·5 H2O
(9.0 g L 1, 99 % Alfa Aesar), and boric acid (30 g L 1, 99 + % Alfa
Aesar). A porous structure was induced by electrochemical etching
of copper from the nickel–copper layer at a constant positive po-
tential for 20 min.[9] The template was finally removed by dissolu-
tion in acetone, leaving a replica in arrangement of a thin film. The
product could then be removed mechanically from the working
electrode.
Porous nickel nanotubes were obtained at similar potentials during
electrodeposition and subsequent electrochemical etching. Howev-
er, the deposition and etching time was set to 400 s and 200 s, re-
spectively. Instead of polystyrene, porous anodized alumina oxide
(AAO), with a pore size of 200 nm, was chosen as the template,
 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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which represents an established procedure for nanowire-array fab-
rication. A thin gold layer was sputtered onto one side of unsup-
ported AAO membranes to make the surface electrically conduc-
tive. A Teflon tape served to protect the AAO-free metallic surface
from the electrolyte. The working electrode was disconnected from
the circuit, washed with distilled water, and the AAO template was
dissolved by treatment with NaOH solution for 1 h. The resulting
free-standing porous-nickel nanotubes stayed attached to the
sputtered gold layer.
Acknowledgements
Electron microscopy was performed at the electron microscopy
center of ETH Zurich (EMEZ). A.S. would like to thank the Swiss
National Science Foundation for his postdoctoral fellowship at
UC Berkeley.
Keywords: alloys · electrodeposition · nanotechnology ·
nickel · porous materials
[1] a) Z.Q. Peng, S. A. Freunberger, Y.H. Chen, P.G. Bruce, Science 2012, 337,
563 – 566; b) Y. G. Guo, J. S. Hu, L. J. Wan, Adv. Mater. 2008, 20, 2878 –
2887.
[2] a) P. N. Bartlett, J. J. Baumberg, P. R. Birkin, M. A. Ghanem, M. C. Netti,
Chem. Mater. 2002, 14, 2199 – 2208; b) R. Szamocki, A. Velichko, F.
Muecklich, S. Reculusa, S. Ravaine, S. Neugebauer, W. Schuhmann, R.
Hempelmann, A. Kuhn, Electrochem. Commun. 2007, 9, 2121 – 2127.
[3] a) A. R. Studart, A. Nelson, B. Iwanovsky, M. Kotyrba, A. A. Kundig, F. H.
Dalla Torre, U. T. Gonzenbach, L. J. Gauckler, J. F. Loffler, J. Mater. Chem.
2012, 22, 820 – 823; b) J. Banhart, Adv. Eng. Mater. 2013, 15, 82 – 111;
c) Y. Conde, J. F. Despois, R. Goodall, A. Marmottant, L. Salvo, C. San
Marchi, A. Mortensen, Adv. Eng. Mater. 2006, 8, 795 – 803.
[4] C. T. Kresge, M. E. Leonowicz, W. J. Roth, J. C. Vartuli, J. S. Beck, Nature
1992, 359, 710 – 712.
[5] a) P. Calleja, J. Esteve, P. Cojocaru, L. Magagnin, E. Valles, E. Gomez, Elec-
trochim. Acta 2012, 62, 381 – 389; b) W. Gao, S. Sattayasamitsathit, K. M.
Manesh, D. Weihs, J. Wang, J. Am. Chem. Soc. 2010, 132, 14403 – 14405.
[6] R. Oriňkov, A. Turoňov, D. Kladekov, M. Glov, R. M. Smith, J. Appl.
Electrochem. 2006, 36, 957 – 972.
[7] M. Jeske, J. W. Schultze, M. Thonissen, H. Munder, Thin Solid Films 1995,
255, 63 – 66.
[8] H. Natter, M. Schmelzer, R. Hempelmann, J. Mater. Res. 1998, 13, 1186 –
1197.
[9] L. Sun, C. L. Chien, P. C. Searson, Chem. Mater. 2004, 16, 3125 – 3129.
[10] a) P. Allongue, L. Cagnon, C. Gomes, A. Gundel, V. Costa, Surf. Sci. 2004,
557, 41 – 56; b) A. Saraby-Reintjes, M. Fleischmann, Electrochim. Acta
1984, 29, 557 – 566; c) E. J. Podlaha, M. Matlosz, D. Landolt, J. Electro-
chem. Soc. 1993, 140, L149 – L151.
[11] E. Chassaing, K. V. Quang, R. Wiart, J. Appl. Electrochem. 1987, 17, 1267 –
1280.
[12] D. M. Tench, J. T. White, J. Electrochem. Soc. 1990, 137, 3061 – 3066.
[13] a) L. B. Hu, H. Wu, F. La Mantia, Y. A. Yang, Y. Cui, ACS Nano 2010, 4,
5843 – 5848; b) T. Ogasawara, A. Debart, M. Holzapfel, P. Novak, P. G.
Bruce, J. Am. Chem. Soc. 2006, 128, 1390 – 1393; c) S. Grugeon, S. Lar-
uelle, L. Dupont, F. Chevallier, P. L. Taberna, P. Simon, L. Gireaud, S. Las-
caud, E. Vidal, B. Yrieix, J. M. Tarascon, Chem. Mater. 2005, 17, 5041 –
5047; d) M. M. Shaijumon, E. Perre, B. Daffos, P. L. Taberna, J. M. Taras-
con, P. Simon, Adv. Mater. 2010, 22, 4978 – 4981.
[14] a) R. C. Furneaux, W. R. Rigby, A. P. Davidson, Nature 1989, 337, 147 –
149; b) H. Masuda, K. Fukuda, Science 1995, 268, 1466 – 1468; c) M. S.
Sander, A. L. Prieto, R. Gronsky, T. Sands, A. M. Stacy, Adv. Mater. 2002,
14, 665 – 667; d) S. Zhao, H. Roberge, A. Yelon, T. Veres, J. Am. Chem.
Soc. 2006, 128, 12352 – 12353.
Received: October 6, 2013
Published online on December 30, 2013
ChemElectroChem 2014, 1, 536 – 538 538