INTRODUCTION

Metals at the nanometer scale exhibit unusual behavior compared to their bulk counterparts. The manifestation of quantum phenomena in the electron transport of metallic nanowires is an example, as are the interesting magnetic properties of nanoparticles (transition metals) due to spin-polarized transport.1,2 Such unusual properties have generated interest in nanostructured materials for potential applications in biomedical sciences, electronics, optics, magnetism, and energy storage.3,4 These nanostructured materials can be synthesized by a number of techniques, such as inert gas condensation, plasma processing, physical and chemical vapor deposition, electrodeposition, mechanical alloying, rapid solidification, sol-gel, micro-emulsion, spark erosion, and severe plastic deformation.5 Although the use of many such techniques is limited to laboratory scale, inert gas condensation, mechanical alloying, and electrodeposition are among the methods that are available for commercial use. In this article, an overview of nanomaterials synthesis using electrodeposition techniques is presented.

ELECTRODEPOSITION TECHNIQUES
The formation of nuclei on the electrode substrate was extensively studied on the basis of macroscopic thermodynamic considerations. The nucleation of nanostructures on the electrode substrate during electrodeposition is influenced by the crystal structure of the substrate, specific free surface energy, adhesion energy, lattice orientation of the electrode surface, and crystallographic lattice mismatch at the nucleus-substrate interface boundary.6,7 The final size distribution of the electrodeposits, however, strongly depends on the kinetics of the nucleation and growth. The electrodeposition process involves the formation of either an instantaneous or a progressive nucleation.8 In the case of instantaneous nucleation, all the nuclei form instantaneously on the electrode substrate, and subsequently grow with the time of electrodeposition. In contrast, the number of nuclei that are formed is a function of time of electrodeposition in the progressive nucleation. These nuclei gradually grow and overlap, and therefore, the progressive nucleation process exhibits zones of reduced nucleation rate around the growing stable nuclei. The electrodeposition method consists of an electrochemical cell and accessories for applying controlled current at a certain voltage. The cell usually contains a reference electrode, a specially designed cathode, and an anode or counter electrode. The cathode substrate on which electrodeposition of the nanostructure takes place can be made of either nonmetallic or metallic materials. Using the surface of the cathode as a template, various desired nanostructures or morphologies can be synthesized for

specific applications. Such a template-assisted electrodeposition process can be broadly divided into two groups: active template-assisted and restrictive templatebased electrodeposition. Active Template-Assisted Electrodeposition The formation of nanostructures in active template-based synthesis results from growth of the nuclei that invariably nucleate at the holes and defects of the electrode substrate. Subsequent growth of these nuclei at the template yields the desired surface morphology of the nanostructures, which can therefore be synthesized by choosing the appropriate surface of the electrode. Highly oriented pyrolitic graphite (HOPG), for example, is used extensively as an electrode substrate for the electrodeposition of silver,911 gold,12 molybdenum,13 palladium,1416 and platinum17 nanostructures. Electrodeposition initiates at the step edges, dislocations, and defect sites of the electrode surface. Vzquez et al.9 studied the early stages of overpotential deposition of silver on HOPG from silver-ion-containing acidic solution. It was shown that the initial deposition occurred at the step edges of the electrode surface, and silver nuclei were not found on the flat HOPG surface domains. The electrodeposition study10 of silver on the HOPG substrate using in-situ scanning tunneling microscopy revealed that at low over-potentials, the deposition process on the atomically flat terraces of HOPG was inhibited because of weak substrate-deposit interaction leading to preferential silver deposition at step edges and other surface defects. Such step-edge deposition involves the preferential nucleation and subsequent growth of nanoparticles on a certain crystal surface. Figure 1 shows a schematic diagram of stepedge synthesis. Favier et al.16 attempted to fabricate hydrogen sensors and switches with the help of palladium nanoparticles electrodeposited onto the graphite step edges. Stable, two dimensionally branched palladium islands, 100160 nm in size, were electrodeposited14 on HOPG from an aqueous acidic palladium chloride solution with an excess of sodium perchlorate at a potential of a few millivolts above the threshold potential of the hydrogen evolution reaction. Platinum nanocrystals were deposited17 on the basal plane of HOPG from dilute (1.0 mM) PtCl6 2- containing electrolytes using a pulsed potentiostatic method. The deposition of platinum nanocrystals occurred via an instantaneous nucleation and diffusion-limited growth mechanism which resulted in a narrow particle size distribution for mean crystallite diameters smaller than 40 . The active template-assisted deposition includes numerous other techniques. Nickel nanoparticles with a narrow size distribution have been electrodeposited on a graphite surface using the hydrogen co-evolution method.18 The electrode position of metal at large overpotential invariably results in instantaneous nucleation, which is nonselective, mostly due to the formation of a large number of nuclei on defect-free terraces as well as at defects such as step edges on the surfaces. The nuclei density is

expected to be of the order of 109cm2. The dependence of the number of nuclei on time was investigated6 in a wide range of voltage intervals using different glassy carbon electrodes. The data for the steady-state nucleation rate were interpreted on the basis of both classical and atomistic concepts of nucleation phenomena. Since electrodeposition occurs at the defect sites, arrays of palladium nanoparticles have been synthesized19 by electrodepositing them on the surface of an aluminum layer obtained from a digital video disc (DVD) that usually has a 50 m thick aluminum layer between two polycarbonate layers. The aluminum layer with arrays of laser holes was exposed by peeling off one polycarbonate layer, and palladium nanoparticles from a palladium chloride solution were electrodeposited on the holes. Pits in the aluminum layer were created during data recording, and palladium nanoparticles preferentially deposited into the pits, making arrays of metallic nanoparticles. The blank aluminum template and the aluminum template with arrays of electrodeposited palladium nanoparticles are depicted in Figures 2a and 2b, respectively.

Figure 2. Scanning-electron micrographs of an aluminum template (a) blank and Figure 3. Scanning electron (b) with electrodeposited arrays of palladium nanoparticles. micrographs of palladium particles on a freshly cleaved graphite surface.

In order to study the role of electrode surface on electrodeposition, palladium nanoparticles were deposited on a freshly cleaved graphite surface.20 A microscopic investigation found that the palladium nanoparticles were faceted and their shape was mostly spherical, as shown in Figure 3. The faceted characteristic of these particles is more clearly observed in the inset of Figure 3. Nuclei formed at almost all parts of the electrode surface; however, the presence of a large number of nanoparticles near the edges and boundaries (Figure 3) indicates a preferential nucleation process.

In another study,21 the growth of the palladium nuclei was found to be at the grain interior during electrodeposition on an AISI 316 grade stainless-steel electrode. It is well known that nucleation occurs preferentially at the holes or disorder state of the substrate on which the metal is to be deposited. Scanning electron micrographs of the surface of the stainless steel after electrodeposition of palladium nanoparticles at low and high magnifications are shown in Figures 4a and 4b, respectively. Although nucleation occurred preferentially at the grain boundaries, the extensive growth took place only for nuclei within the grain interior, as shown in Figure 4b. The probable reason for the discrepancy in deposition of palladium particles on the grain rather than on the grain boundary is the presence of oxide ridges at the grain boundaries where the formation of chromium oxide is easy at room temperature. Stainless steel consists of 18 wt.% chromium, which forms thin film oxides at room temperature. The oxidation process is more favorable at the grain boundaries because the formation of oxide nuclei at room temperature is energetically favorable due to the presence of defects. Although the formation of nuclei on such stainless-steel templates during electrodeposition of palladium was easy, subsequent growth of nuclei on top of the oxide ridge at the grain boundaries of the steel substrate was slow compared to that of the nuclei at the grain interior. The slow growth rate was attributed to the difficulty in the charge transfer due to the presence of highly resistive oxide film underneath the nuclei at the grain boundaries of the stainless-steel template.

b Figure 5. A scanning electron micrograph of palladium particles on carbon tape.

Figure 4. Scanning electron micrographs (a) bare and (b) palladiumdeposited stainless-steel surfaces after thermal etching.

Figure 5 presents the role of amorphous carbon substrate as a template for the electrodeposition of palladium nanoparticles.20 Although the template consists of carbon, the shape of the electrodeposited metallic particle differs from that of the cleaved graphite surface. In the case of the amorphous carbon substrate, the nuclei formed at random locations and fractal growth behavior was observed. In addition, the

attachment between the deposits and carbon substrate was weak. All these results strongly indicate that the surface of the active template plays an important role in shape and size distribution of metallic nanoparticles during electrodeposition. Table I presents the various active template substrates used for template-assisted electrodeposition of metallic nanostructures of mostly precious metals such as silver, gold, platinum, and palladium.
Table I. Various Active-Template Substrates Used for Electrodeposition of Metallic Nanostructures Template Substrate Highly oriented pyrolytic graphite (HOPG) Au Mo Pd Elements Deposited Ag Size and Shape of Nanostructures Flat island of diameter 0.29 nm Clusters of 10 nm diameter Disc (diameter 2060 nm and height 1.55 nm) Aggregate (size 500 nm and height 70 nm) Nanowire of 15 nm diameter Island of 200300 nm grain size range Two-dimensional branched island (100160 nm) Mesowires of grain size 50300 nm Pt Graphite surface Al foil with laser hole Stainless-steel grain interior Carbon tape Pd Ni Pd Pd Pd Spherical particles of 20600 nm size Arrays of nanoparticles with 5 nm diameter Agglomerated particles (average size 70 nm) Meso-sized particles Ref. 9 10 11 12 13 15 14 16 17 20 18 19 21 20

Restrictive Template-Based Electrodeposition Another template-assisted synthesis of mostly metal nanowires involves the deposition of metal into the cylindrical pores or channels of an inert, nonconductive nanoporous electrode material. Track-etch membranes,22 porous alumina,23 and other nanoporous structures including conductive polymers, metals, semiconductors, carbons, and other solid materials have been used as templates to prepare nanometersized particles, fibrils, rods, and tubules. Various electrode substrates used for restrictive template-assisted electrodeposition of metallic nanostructures are presented in Table II.
Table II. Various Restrictive Template Substrates Used for Electrodeposition of Metallic Nanostructures Template Substrate Deposited Size and Shape of Nanostructures Ref.

Nanoindented holes Polyethylene glycol and polyvinyl pyrrolidone Semiconductor InAs quantum well Mesoporous silica

Ni-Fe island Nanostructured Pd

Diameter of 5 nm Surface areas 50 m2g1

26 24

Magnetic nanowires Co nanowires Ni and Co Pd nanowire

Magnetic nanowire of width 20 nm Dimension is not reported Nanowires with 30 nm diameter Diameter of 7 nm

25 29 27 28

Palladium deposits with high specific surface areas, up to 50 m2g1, have been synthesized24 from palladium chloride solutions with additions of polyethylene glycol and polyvinyl pyrrolidone. Details of the globular structure of the deposits depend on the polymer additives. A comparison with electrochemically determined true surface areas demonstrates the rare coalescence of nanoparticles. Fasol and Runge25 deposited magnetic permalloy (NiFe) nanowires on the edge of an InAs quantum well. Carrey et al.26 used a nanoindented Al2O3-Al foil to preferentially electrodeposit Ni-Fe nanoparticulate arrays from an electrodeposition bath containing a solution of nickel and iron sulfate. Fabrications of arrays of nickel and cobalt nanowires have been reported through electrodeposition at constant potential by Whitney et al.27 In order to fabricate arrays of nanowires on a polycarbonate porous membrane, a copper film was first sputter-deposited to make the working electrode. The electrodeposition Figure 6. A schematic electrode arrangement for the synthesis of solution was confined to the bare side of the nanowires though restrictive templatemembrane so that deposition was initiated onto the assisted electrodeposition. copper film through the pores. It was observed27 that the electrodeposition current was directly proportional to the area of electrodeposits at any given potential under a pseudosteady-state condition. Thin films composed of ordered arrays of palladium nanowires have been electrochemically synthesized28 using silica mesoporous channels. The experimental set-up showing the electrochemical cell along with a restrictive template for electrodeposition is schematically presented in Figure 6. Mesoporous channels have been deposited on a conductive glass substrate. In this method, nanowires with

the face-centered-cubic crystal structure (Fm3m) are continuously deposited from the conductive substrate upward until the mesoporous channels are filled.

MORPHOLOGY AND CHARACTERIZATION OF DEPOSITS

The surface morphology of the electrodeposits depends on the structure and chemical composition of the electrode surface as well as other electrochemical parameters. The morphologies of the nanostructures prepared using electrodeposition techniques are usually characterized using transmission electron microscopy and non-contact atomic force microscopy. The electrodeposition of gold12 on HOPG from acidic aqueous solutions was studied by using electrochemical techniques complemented with ex-situ scanning tunneling microscopy. The kinetics of gold electrodeposition are consistent with a nucleation and three-dimensional growth process. A model including a potential-dependent energy barrier at step edges accounts for the morphology transition for gold electrodeposition on HOPG. It was shown12 that dendritic aggregates are produced when the gold surface is negatively charged at potential less than the potential of zero charge. Such growth behavior results from the anisotropic corner surface diffusion caused by the varying energy barriers for the diffusion of surface atoms at step edges, as has been observed for metal deposition from vapor. Rounded kinked gold crystals are formed when the gold surface is positively charged at potential greater than the potential of zero charge. This was attributed to the leveling and lowering of barrier heights at step edges induced by Cl ion adsorption on gold aggregates. A potentiostatic-pulse method was used11 to electrochemically deposit silver nanocrystallites on the atomically smooth graphite basal-plane surface. The particles were disc-shaped and well separated, with a height of 1.55 nm and an apparent diameter of 2060 nm. It has been often found that the result of electrodeposition using a carbon substrate is weaker than that with a metallic substrate. The surface morphologies of the nanostructures that are formed on carbon substrates have been found to be faceted.

CONCLUSION
Template-assisted electrodeposition is a versatile technique to synthesize various kinds of arrays, nanoparticles, and nanowires with a desired structure. Its flexibility gives the opportunity to have nanomaterials of desired surface morphologies. The synthesis of nanostructures using template-assisted electrodeposition is an emerging area in nanoscience and technology with the possibility of numerous applications in micro and nanodevices. Although a variety of templates and

electrodeposition processes are reported in the literature, the universal application of such templates for depositing metallic nanostructures with controlled and well-defined morphologies is missing. The major problem with using electrodeposition to synthesize nanostructure is the preparation of proper templates. Electrodeposition is highly influenced by the surface characteristics of the electrode substrate, and the shape and size of the deposit depend on the substrate. Therefore, further study of electrode surfaces and subsequent surface engineering are essential to develop active templates for the successful synthesis of nanostructures using electrodeposition. In order to understand the preferential deposition on a particular site of the electrode substrate, further studies on the fundamentals of the nucleation and growth of nanoparticles are needed.

1 Introduction

There is a need for alternative fuels because of limited oil supply,(1) increased oil demand,(1)and persistent increase in oil prices.(2) One alternative fuel/additive is a mixture of methanol and higher alcohols. Another important application of this mixture is that it can be used for transporting hydrogen. These alcohols can then be steam reformed or partially oxidized to produce a hydrogen-rich reformate.(3-5) One of the ways to produce these alcohols is via catalytic conversion of CO and H 2. To date, rhodium-based catalysts have been the most promising but their prohibitive cost and limited supply hinder their ability to be used as industrial catalysts.(6) Thus, much less expensive Cubased catalysts(7, 8) are an attractive option. Generally, heterogeneous catalysts are prepared by conventional methods such as coprecipitation and impregnation. To further increase the selectivity of these catalysts toward desired products, novel methods that can engineer the surface and molecular environment of the catalysts, are needed. Novel catalyst preparation methods have been found to be promising.(9-11) One such method is pulse electrodeposition of nanowires/tubes.(12, 13) This method consists of a number of independent synthesis variables

(electrolyte composition, temperature, pulse schemes, etc.) that allows better control over surface properties of multimetallic catalysts than conventional methods. Fabrication of one-dimensional (1D) metals and metal oxide nanostructures are the subject of increasing attention due to their distinct properties compared with the corresponding bulk materials.(14-16) The two main reasons for these distinct properties(17, 18) are as follows: (1) an increased surface to volume ratio which results in corresponding increase in their activity as catalysts and (2) the dominance of quantum effects which significantly changes a materials optical, magnetic, or electrical properties.(19-21) Diversified synthesis techniques including lithography,(17) molecular beam epitaxy (MBE),(22)thermal evaporation,(23) ion beam sputtering,(24) chemical vapor deposition,(2527) pulse laser deposition,(28) vaporliquidsolid (VLS) mechanism,(29) solgel method,(30) pulse electrodeposition of nanowires/tubes,(13, 31) surfactant-assisted growth,(32) and hydrothermal approach,(33, 34) have been employed to synthesize these nanostructures. Electrodeposition is one of the promising technologies because of its versatility and suitability for deposition in trenches of small dimensions. Electrodeposition can be used to control the aspect ratio (length-todiameter ratio) of the metal nanowires by monitoring the total amount of passed charge, which is not possible with other methods.(35, 36) Nanowires with multiple segments of different metal/alloys in a controlled sequence can be fabricated by applying suitable current/potential (pulse electrodeposition) in an electrolyte solution containing different metal ions. However, careful selection of electrolytes, additives, and pulse schemes is necessary when elements have very large difference in their reduction potentials such as Cu and Co. The template-based approach has been extensively investigated to fabricate nanowires/tubes. Possin reported the electrodeposition of Sn, In, and Zn nanowires using radiation track etched mica membranes for the first time.(37) A comprehensive overview of the template based preparation of wide variety of nanowires including metals, polymers, semiconductors, and carbon with detailed chemistry had been explored by various researchers.(38-40) Individual metal/oxide nanowires of Co, Cu, and Zn had been fabricated by several research groups using variety of templates due to its promising applications in piezoelectric devices, sensors, and solar cells.(41-48) Combination of such metal/oxide nanowires might yield novel materials having superior applications. For example, Oh et al.(49) electrochemically deposited n-p and/or p-n nanocolumnar junction structures of Cu2O, ZnO, on Ni nanowires using a commercially available alumina template.

In one of our previous works, nanowires of Cu-ZnO and MnCuZnO(50) were synthesized by pulse and direct electrodeposition. These nanowires were active catalysts for the synthesis of alcohols from CO hydrogenation. MnCuZnO nanowire catalysts seem to be promising because of high selectivity (15.7%) toward higher alcohols at low reaction pressure (10 bar). Addition of manganese to CuZnO nanowires increased the selectivity toward C2C4 alcohols from 5.4% to 15.7%, while suppressing the formation of methane. Here, we chose CoCuZnO because these types of catalysts have shown to be promising for mixed alcohols. However, there is no clear consensus on how Co and Cu interact. Pure Cu catalysts adsorb CO associatively and are well-known for synthesis of methanol;(51) whereas pure Co catalysts adsorb CO dissociatively and are active for the synthesis of hydrocarbons.(52)Because both types of CO adsorption are needed to form higher alcohols, intimate mixing of Co and Cu atoms holds promise for the formation of higher alcohols,(53) possibly by interaction between Co and Cu to form a CoCu surface alloy.(54) Several researchers have found CoCuZnO catalysts to be promising for ethanol and higher alcohols.(53, 55, 56) In the present study, we synthesized, characterized, and tested (as catalysts) CoCuZnO nanowires/tubes using electrodeposition into nanopores of polycarbonate track etch (PCTE) membranes.(57, 58)

2 Experimental Section

Polycarbonate track etch (PCTE) membranes (Sterlitech Corporation, WA), having an average pore diameter of 400 nm and thickness of ca. 25 m, were used as templates for the synthesis of Co CuZnO nanowires/tubes via pulse electrodeposition. Experiments were carried out in a typical three-electrode cell.(50) A thin gold film was sputter coated on one side of the membrane which later served as the working electrode for the pulse electrodeposition process. The coated membrane with open pores facing upward was placed on a Cu plate held inside a polyetheretherketone (PEEK) holder. The deposition of nanowires takes place inside these pores. The counter electrode and the reference electrode were a platinized Ti-mesh and a saturated calomel electrode (SCE), respectively. The three electrode holder was immersed in a 5 L container, the whole assembly served as the electrochemical cell. It was filled with freshly prepared electrolyte containing nitrates of Co, Cu, and Zn dissolved in deionized water at room

temperature. More details about the experimental setup and method can be found in this work.(50) The composition and pH of the electrolyte solution used in this work are shown in Table 1. The electrolyte was magnetically stirred at 320 rpm. The cell was kept inside a water bath to maintain the temperature of the electrolyte solution at 60 2 C. All of the experiments were carried out with a VersaSTAT3 potentiostat/galvanostat (AMETEK Princeton Applied Research, TN). Three types of current pulse schemes were applied in order to obtain different metal/oxide compositions and atomic environments. A low current to deposit Cu, followed by a high current to deposit Co and then an off-time was given to allow the ions to be replenished near the cathode. Figure 1 is an example of one of the pulse schemes used and Table 2 gives all of the details of the pulses applied.

Figure 1. Pulse scheme.

Table 1. Composition of the Electrolyte

electrolyteinitial pHCu(NO3)2 (M)Zn(NO3)2 (M)Co(NO3)2(M)

CoCuZn

4.2

0.002

0.025

0.01

Table 2. Detailed Pulse Schemes

catalystlow current density (mA/cm2) /time(ms)high current density (mA/cm2) /time(ms)off-time (ms)

6.9/300

11.5/500

1200

catalystlow current density (mA/cm2) /time(ms)high current density (mA/cm2) /time(ms)off-time (ms)

6.9/300

11.5/600

1200

6.9/300

11.5/750

1200

After the electrodeposition experiment, membranes were dissolved in methylene chloride (CH2Cl2) and then sonicated to separate the entangled nanowires/tubes. Nanowires were separated from CH2Cl2 by centrifugation and then using acetone they were transferred to aluminum dishes. The nanowires were then dried in the oven at 110 C for 12 h. Imaging and compositional analyses were performed using a Hitachi HF3300 high-resolution transmission-scanning transmission electron microscope (TEM/STEM), which was operated at 300 kV. This instrument is also equipped with a secondary electron detector (SE) and a Bruker X-Flash silicon drift detector (SDD) for energy dispersive spectrometry (EDS). Samples for TEM were prepared by embedding the nanowires in epoxy (Gatan G-1) and placing between two silicon wafers. Cross sections of this sandwich structure were prepared by mechanically grinding, dimpling, and ion milling to perforation such that several thin, individual nanowires could be viewed longitudinally and in cross-section. Bulk elemental compositions were determined using a Perkin-Elmer 2000 DV ICP-OES. X-ray diffraction (XRD) patterns were obtained with an automated X-ray powder diffractometer (Bruker/Siemens D5000, Cu K radiation). XPS analyses were done using a ThermoScientific model K- X-ray Photoelectron Spectrometer (XPS) system. Samples were mounted onto nonconducting double-sided tape which were fixed to glass slides. Mounted samples were introduced into the XPS analysis chamber (base pressure 6 1010 mbar) though a turbopumped load-lock. Experiments were conducted using monochromatic Al-K X-rays and detecting photoemitted electrons using a hemispherical electron energy analyzer and multichannel plate detector. Survey spectra were collected at a pass energy of 200 eV over the range 01300 eV binding energy, while core level spectra were collected at 50 eV pass energy. Sample charging induced by the photoemission process was alleviated using a charge compensation system consisting of both low energy Ar-ion and low energy electrons.

CO hydrogenation studies were performed in a tubular fixed bed reactor (AMI-200R-HP) manufactured by Altamira Instruments, Inc. Catalysts were placed inside a glass lined reactor tube (0.25 OD, 0.15 ID, 12 length) using quartz wool. First, 10% O2 in He was passed through the catalyst for 2 h at 400 C to oxidize any carbon left after dissolution of the polycarbonate membrane. Then, the catalyst (physically mixed with -Al2O3 supplied by Alfa Aesar) was reduced using 100% H2 at 320 C for 2 h. The reaction was performed at 15 bar, H2/CO = 3/1, GHSV = 16000 scc/h gcat, and 270 C. The product stream was analyzed by a GC-FID (GC-2014) manufactured and supplied by Shimadzu Scientific Instruments, Inc.

3 Results and Discussion

The electrodeposition of different elements (such as Cu and Co) with desired composition is difficult because they have disparate reduction potentials. In addition to these two elements, we have deposition of ZnO which makes it even more complex because ZnO deposits chemically rather electrochemically.(59, 60)To achieve desired composition of the nanowires/tubes, it is necessary to know the different reactions occurring at the cathode in the potential range studied. Figure 2 shows the polarization curve for the electrolyte used to electrodeposit nanowires/tubes using a gold sputtered membrane as a cathode. The potential scan rate was 10 mV/s. Region A corresponds to the electrodeposition of Cu in kinetically controlled regime. All the potentials reported in the present study are the reversible electrode potential (E) vs SCE, calculated using the Nernst equation. The deposition of Cu takes place through the following reaction: (1)where E is the reversible reduction potential.

Figure 2. Polarization for the CoCuZn electrolyte using a gold sputter coated membrane.

Region B has a plateau that is indicative of the mass transport controlled deposition of Cu. The following side reaction could also occur in this region: (2)

Region C represents the sudden increase in current after 0.54 V, which could be due to following reactions: (5) The following undesirable reaction can also take place in this region. Mainly, this is the reduction of water to form hydrogen. (6) (3) (4)

At the electrode surface, the pH of the solution changes from acidic to alkaline due to the reduction of nitrate ions.(59, 61, 62) In fact, Zhang et al.(61) performed the in situexperiments using a microsensor and found that the local pH at the electrode increased from 4.5 to 8.3 during the electrodeposition of mixed Er-ZnO/(OH)2 using a nitrate electrolyte possibly due to the following reaction: (7)

Deposition of ZnO is not electrochemical rather chemical. Therefore, it cannot be represented by any of the regions of the polarization curve. ZnO is deposited in the nanowires/tubes via the following reaction sequence:(59, 60) (8) (9)

The above reactions and their corresponding E values give an idea to construct pulse schemes (Figure 1, Table 2) to achieve desired morphology and concentrations. First, a low current was applied to deposit Cu (major) and Co (minor) and then a high current density was applied to deposit Co. ZnO will be deposited both times because of the pH change.(13) An off-time was given to allow ions to replenish on the cathode.