DEVELOPMENT OF CATHODE MATERIAL FOR ELECTROCHEMICAL

DENITRIFICATION OF LANDFILL LEACHATE

S.T. Kariyawasm, M.K.D.C.S. Meegoda, Dr. K.G.N Nanayakkara
Department of Civil Engineering, University of Peradeniya

. A cathode material was developed in order to remove nitrates from landfill leachate

electrochemically by plating Cu on Al and mild steel substrates. An EDTA plating

bath was used for electroless deposition of Cu on the substrate material. The varied
HCOH concentrations in the plating bath resulted in a successful coating of Cu on
the Al substrate only. The developed Al electrodes were subjected to
characterization tests. It was found that higher concentrations of HCOH increased
the electroless plating rate and also resulted in the formation of smaller grains on
the Cu deposit which was confirmed by SEM images. The developed cathodes
were coupled with a Ti anode and employed to denitrify a synthetic leachate
sample. A percentage nitrate removal greater than 98% was achieved by all the
plated Cu cathodes compared to 74% achieved by a pure Cu cathode. However, a
significant difference in percentage nitrate removal was not observed among
developed cathodes.

2.25

Preparation of
plating bath

Shaping
Cleaning
Etching

Average Plating Rate of copper x10-5

( g/cm2.hr)

ABSTRACT

Surface preparation

Electroless
plating

Fig. 2: Electroless copper plating

Table 1: Removal of nitrate by pure and developed

electrodes

2.2
2.15
2.1

Initial

2.05
2
1.95

Electrode

1.9
1.85
0

0.1

0.2

Concentration of HCOH

0.3

0.4

Fig. 4: Variation of the average plating rate with

the formaldehyde concentration for Al substrate

0.2M HCOH

Denitrification
of synthetic
leachate

electrode

0.3M HCOH
electrode

Electroless plating
In contrast to the Al substrate, the mild steel electrodes did not show any mass gain of Cu for 0.11 M EDTA
and 0.05 M CuNO3 plating solution at the room temperature. The test was repeated at a steady temperature
of 58oC using the same plating solutions but the mass gain of Cu was insignificant. The concentrations of the
plating solution were increased tenfold up to 1 M EDTA and 0.5 M CuNO3, but still there was no mass gain
in steel electrodes at room temperature nor at 58oC. Since it was unable to get a sufficient plating of Cu on
the mild steel electrodes electrochemical denitrification was carried out using plated Al electrodes only. The
average plating rate of Al increased with the increasing formaldehyde concentration as shown in Fig. 4
Characterization of the electrodes with Scanning electron microscope

NO3- +H2O+2e- NO2- +2OHNO2- +2H2O+3e- N2 +4OH-

METHOD
Aluminum and steel sheets were shaped into electrodes of 1 cm X 1cm to be prepared for
electroless plating. Electrodes were plated using a plating bath of 0.11M EDTA, 0.05M
CuSO4 & NaOH. 0.1M, 0.2M and 0.3M formaldehyde solutions of varied concentrations were
used as the reducing agent in electroless plating of both substrates. Plating was carried at room
temperature as shown in Fig.2. Plated electrodes were characterized using cyclic voltammetry
(CV) and morphological analysis. Ti electrode was used as the counter electrode and saturated
calomel electrode was used as the Reference electrode in CV . Under morphological analysis
the electrodes were examined using a scanning electron micro-scope (SEM) and the surface
composition was detected using Energy Dispersive X-ray (EDX) analyzer. Then the developed
electrodes were used to denitrify synthetic leachate sample (shown in Fig.3) and the nitrate
removal percentage was determined by measuring nitrate concentration before and after
denitrification using spectrophotometry method. Aforementioned characterizations and
denitrification was done using a pure Cu electrode as a comparison

(A)

(B)

(ppm)

percentage

73.3%

Below the

>98%

15
detection limit
15

(Detection

(C)

(D)

>98%

mg/L)
15

Under range

Fig. 6:Variation of charge vs. potential of

plated electrodes and pure electrodes

NO3- +3H2O+5e- N2 +6OH-

NO3- +6H2O+8e- NH3 +9OHThe developed cathodes were characterized using scanning electron microscope and EDX in
order to study the surface morphology and composition respectively. The active surface area
was compared by cyclic voltammetric analysis. The denitrification process was conducted on
a synthetic leachate sample to investigate the percentage nitrate removal of each developed
cathode.

removal

15

Fig 3. Electrochemical denitrification

RESULTS

INTRODUCTION

concentration

limit: 0.3

Fig. 1: Methodology

Majority of the solid waste produced ultimately end up in dumpsites. Leachate produced by
such dumpsites contain high levels of NO3-, which contaminates water and soil and could
cause diseases to humans. Thus nitrates in leachate have to be treated before disposal.
Treatment of nitrates using electrochemical methods is efficient and cost effective.
Efficiency of electrochemical methods could be amplified further by developing new
electrode materials. This study focused on developing a cathode using a low cost substrate
material by electroless deposition of Cu.
At the cathode surface NO3- reduces to nitrogen gas which is a harmless product but
ammonia and nitrite is also formed as intermediate products. Nitrites formed are further
reduced to N2 at the cathode as expressed by the equations below.

Pure copper

electrode
Cyclic voltammetry
SEM
EDX

concentrati

Nitrate

on (ppm)

(mol/dm3)

0.1 M HCOH

Characterization

nitrate

Final nitrate

>98%

CONCLUSIONS
In this study it was identified that the electroless Cu deposition rate on Al increases with the
HCOH concentration. SEM images confirmed that higher concentrations of HCOH results in
the formation of smaller grains of deposited Cu up to 2m in diameter. This agrees with the
SEM images obtained by Sha et al. (2011).
Cyclicvoltammograms revealed that surface charge on pure Cu electrode is much higher than
that on the developed Al electrodes. This indicates that the pure Cu electrode has a much higher
active surface area than the developed electrodes which directly contradicts with the findings of
Norkus et al. (2006) and visual observation of SEM images. The surface charge on the
developed cathodes may have reduced due to the formation of CuO on the surface and this
requires further investigation.
The developed electrodes were successful in reducing the nitrates from the synthetic sample. A
percentage reduction of nitrate concentrations greater than 98% was achieved by using the
developed cathodes marginally greater than that achieved by the pure Cu cathode. However the
final nitrate concentrations of the treated leachate couldnt be quantified accurately due to the
limitation of the range in spectrophotometer.

Fig. 5: The SEM images of the morphology of the copper plated cathode in bathes (A) 0.1M HOCH, (B)
0.2M HOCH, (C) 0.3M HCOH and (D) pure copper at a magnification of 5000X
The SEM images showed that the size of the grains reduce its size and the size and the number of dimples in
the structure is reduced with the increasing formaldehyde concentration.SEM also images implies that the
electro deposition gives a coarser surface than the pure Cu metal surface. This results shows that the HCOH
concentration has a significant impact on the surface texture.
Characterization of electrodes with cyclic voltammetry

It can be shown that surface area of the electrode could be obtained indirectly by referring to the
cyclicvoltagrams according to Randles-Sevicik equation at 250C.At constant concentration of electrolyte and
the scan rate charge would be directly proportional to the active surface area of the electrode. Fig. 6 shows
the charge vs potential curves obtained for plated electrodes and pure electrodes. According to results
obtained under this experiments shows that Cu has the highest active area.
Denitrification of synthetic leachate

The table 1 shows the nitrate concentrations of the leachate samples before and after the electrochemical
denitrification.The results indicate that the nitrate concentration has dropped during the electrochemical
denitrification and also it confirms that the developed cathodes are more successful than the pure Cu
electrode in denitrification

REFERENCES
Norkus, E, 2006. Obtaining of high surface roughness copper deposits by electroless plating technique. , 51, pp.3495
3499.
Sha, W., Wu, X. & Keong, K.G., 2011. Electroless Copper and Nickel-Phosphorus Plating: Processing, Characterisation
and Modelling 1st editio., Limited, Woodhead Publishing

ACKNOWLEDGEMENTS
The authors are grateful to Tokyo Cement Company (Lanka) PLC and
The University of Peradeniya for financing the project