The Ni-deposited carbon felt as substrate for preparation of Pt-modified electrocatalysts: Application for alkaline water electrolysis

doi:10.1016/j.ijhydene.2012.03.008

International Journal of Hydrogen Energy

Volume 37, Issue 11, June 2012, Pages 8917-8922

https://doi.org/10.1016/j.ijhydene.2012.03.008 Get rights and content

Abstract

A Ni-modified carbon felt (C) electrode (C/Ni) was used as a substrate for preparation of Pt-modified electrode in view of its possible application as electrocatalytic material for the hydrogen evolution activity. The prepared electrode was characterized by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX) and cyclic voltammetry (CV) techniques. The hydrogen evolution activity of the electrode was assessed by cathodic current–potential curves and electrochemical impedance spectroscopy (EIS) techniques. It was found that the modification of Ni-deposited C by loading low amount of Pt could enhance the hydrogen evolution activity of the electrode.

Graphical abstract

Pt was loaded over the previously Ni-deposited carbon felt substrate and characterized in view of its possible application as electrocatalytic material for the hydrogen evolution activity.

Highlights

► Pt was loaded over the previously Ni-deposited carbon felt. ► The catalyst prepared has spacious volume. ► The Pt loading can further enhance the HER activity of Ni-deposited carbon felt.

Introduction

The electrolysis of water is one of the most promising methods for production of hydrogen [1]. The electricity needed for electrolysis could be supplied by renewable energy sources. The main commercial superiority of hydrogen production by electrolysis through renewable energy sources are its scalability and emission-free production of hydrogen. This method supplies hydrogen of a very high purity in large-scale. The high production cost, low electrode efficiency and the energy consumption, which is directly proportional with cell voltage applied to electrolysis system, are the main drawbacks of this method. In order to make this method more efficient and economical, selecting inexpensive electrode materials, which have high electrochemical activity, good time stability and low overpotential, are needed. The efforts are being devoted to develop new and cheaper electrode materials with higher hydrogen evolution activity and reduce the cost of production.

In literature, various binary and ternary alloys of transition metals i.e. NiCo [2], [3], [4], NiFe [5], [6], [7], [8], NiCu [9], NiCoFe [10], NiFeC [11], [12] have been reported. More attention has been devoted to Raney-type electrodes, which are obtained by selective leaching active metals as Zn and Al metals from alloys or composite materials [13], [14], [15], [16], [17], [18]. The modification of transition metals by co-deposition of noble metals have also been reported [19], [20], [21]. Over the last few decades, some noble metals (i.e. Pt, Rh, Ru) have been regarded as ideal catalysts for hydrogen evolution reaction because of their high catalytic activity, low over potential, selectivity and good electrochemical stability [22], [23], [24]. Unfortunately, these metals cannot be used for practical applications due to their high cost and low abundance. To overcome these disadvantages, it is essential to replace or reduce the dosage of noble metals [25]. The supporting materials with high surface area are essential to reduce the dosage of metal loading. We have previously reported Raney-type electrode materials, CoZn [26] and NiCoZn [27] as supporting materials for platinum group metals. Because C has low cost and has high surface area, it could be used as supporting material for preparation of catalytic electrodes. Although multi-walled carbon nanotubes are being used for the similar applications, these materials are very expensive.

Section snippets

Experimental

C substrates with 10 × 10 × 5 mm dimensions and the average weight of 0.05 g were used as substrate. The physical characteristics of C are; average weight: 220 g m⁻², specific electrical resistance: 0.35 Ω cm⁻¹, average fiber diameter: 9 μm, space volume: 95%. The C samples were carefully washed with distilled water, dried in an oven and kept in a desiccator before measurements. The electrodeposition of metals was performed galvanostatically using a Matrix Model MPS-3003L-3 DC apparatus. The

Characterization of catalysts

The SEM image of C is given in Fig. 1a. As it is seen from Fig. 1a, C sample contains fibers with average 9 μm diameters and spacious space which is an advantage for diffusion of ions and hydrogen bubbles through inner zones and reduction of diffusion resistance. Fig. 1b shows the micrograph of C/Ni–Pt sample. It is clear from Fig. 1b that an adherent layer is formed over the C surface.

The distribution of Ni and Pt metals over the C/Ni–Pt catalyst was examined by EDX. The EDX mapping for Ni and

Conclusions

Low amount of Pt was loaded over the Ni-modified C/Ni substrate and characterized in view of its possible application in alkaline water electrolysis. From the data obtained, the following results can be concluded:

1)
The SEM images showed that, C sample contains thin fibers and spacious space which is an advantage for diffusion of ions and hydrogen bubbles through inner zones and reduction of diffusion resistance.
2)
Ni and Pt metals were homogenously distributed over the substrate. The amount of Pt is

Acknowledgements

This study has been financially supported by the Bingöl University Scientific Research Projects (BÜBAP) Coordination Unit (Project Number: BAP-52-59-2011). The authors are greatly thankful to BÜBAP. The authors are also greatly thankful to Prof. Mustafa Çulha (Yeditepe University) for SEM analysis.

References (37)

C. Lupi et al.
Nickel–cobalt electrodeposited alloys for hydrogen evolution in alkaline media
Int J Hydrogen Energy
(2009)
C.-C. Hu et al.
Bipolar performance of electroplated iron-nickel deposits for water electrolysis
Meter Chem Phys
(2003)
R. Simpraga et al.
In site determination of the ‘real area factor’ in H₂ evolution electrocatalysis at porous Ni-Fe composite electrodes
J Electroanal Chem
(1997)
H.B. Suffredini et al.
Recent developments in electrode materials for alkaline water electrolysis
Int J Hydrogen Energy
(2000)
R. Solmaz et al.
The stability of hydrogen evolution activity and corrosion behavior of NiCu coatings with long-term electrolysis in alkaline solution
Int J Hydrogen Energy
(2009)
M. Jafarian et al.
Kinetics and electrocatalytic behavior of nanocrystalline CoNiFe alloy in hydrogen evolution reaction
Int J Hydrogen Energy
(2007)
L.J. Song et al.
Effect of carbon content on Ni–Fe–C electrodes for hydrogen evolution reaction in seawater
Int J Hydrogen Energy
(2010)
N. Jiang et al.
Study on Ni–Fe–C cathode for hydrogen evolution from seawater electrolysis
Int J Hydrogen Energy
(2010)
R. Solmaz et al.
Preparation, characterization and application of alkaline leached CuNiZn ternary coatings for long-term electrolysis in alkaline solution
Int J Hydrogen Energy
(2010)
B. Losiewicz et al.
The structure, morphology and electrochemical impedance study of the hydrogen evolution reaction on the modified nickel electrodes
Int J Hydrogen Energy
(2004)

M.V. Ananth et al.

Hydrogen evolution characteristics of electrodeposited Ni-Zn-Fe coatings in alkaline solutions

Int J Hydrogen Energy

(1997)

M.J. Giz et al.

NiFeZn codeposit as a cathode material for the production of hydrogen by water electrolysis

Int J Hydrogen Energy

(2000)

F.C. Crnkovic et al.

Electrochemical and morphological studies of electrodeposited Ni-Fe-Mo-Zn alloys tailored for water electrolysis

Int J Hydrogen Energy

(2004)

C.C. Hu et al.

Optimization of the hydrogen evolution activity on zinc-nickel deposits using experimental strategies

Electrochim Acta

(2003)

L. Vázquez-Gómez et al.

Hydrogen evolution on porous Ni cathodes modified by spontaneous deposition of Ru or Ir

Electrochim Acta

(2008)

I. Bianchi et al.

Electrocatalytic activation of Ni for H₂ evolution by spontaneous deposition of Ru

Chem Phys

(2005)

J.B. Raoof et al.

Fabrication of bimetallic CuPt nanoparticles modified glassy carbon electrode and its catalytic activity toward hydrogen evolution reaction

Int J Hydrogen Energy

(2010)

J.B. Yadav et al.

Low Pt loading, wide area electrospray deposition technique for highly efficient hydrogen evolving electrode in photoelectrochemical cell

Int J Hydrogen Energy

(2010)

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The Ni-deposited carbon felt as substrate for preparation of Pt-modified electrocatalysts: Application for alkaline water electrolysis

Abstract

Graphical abstract

Highlights

Introduction

Section snippets

Experimental

Characterization of catalysts

Conclusions

Acknowledgements

Int J Hydrogen Energy

Meter Chem Phys

J Electroanal Chem

Int J Hydrogen Energy

Int J Hydrogen Energy

Int J Hydrogen Energy

Int J Hydrogen Energy

Int J Hydrogen Energy

Int J Hydrogen Energy

Int J Hydrogen Energy

Int J Hydrogen Energy

Int J Hydrogen Energy

Int J Hydrogen Energy

Electrochim Acta

Electrochim Acta

Chem Phys

Int J Hydrogen Energy

Int J Hydrogen Energy