Square wave anodic stripping voltammetry of

copper(II) at a tetracarbonylmolybdenum(0)
MWCNT paste electrode
PROFESSOR ILLYAS MD ISA
MOHAMAD IDRIS SAIDIN
UNIVERSITI PENDIDIKAN SULTAN IDRIS, MALAYSIA

INTRODUCTION
Copper
Used for many industrial, agricultural and domestic purposes and also plays an
important role in various biological processes.

Effect

Available methods
Atomic absorption
spectrometry (AAS)

Inductively coupled plasmaoptical emission spectroscopy

(ICP-OES)

Inductively coupled plasmamass spectrometry (ICPMS)

Expensive instruments, time consuming, require adequate

expertise, maintenance and operational cost is high.

Electrochemical sensor

Square wave anodic stripping voltammetry (SWASV) have been recognized as a powerful
technique for electrochemical measurements of trace metal ions in various samples, in
particular due to its speed of analysis, good selectivity, and sensitivity.

Modified multiwalled carbon nanotube paste electrode

Objective of study

To develop multiwalled carbon nanotube (MWCNT) modified paste electrodes by

using
tetracarbonylmolybdenum(0).

To study the SWASV behavior of copper(II) on proposed electrodes.

To study the chronocoulometry and electrochemical impedance spectroscopy (EIS) of

proposed electrodes.

To determine copper(II) in various samples by using the proposed electrodes.

Methodolgy
Synthesis of
tetracarbonylmolybdenum(0) complex

Analytical application
to water samples

Electrochemical
impedance
spectroscopy studies

Preparation of MWCNT
modified paste electrodes

SWASV behavior of
copper(II) on
proposed electrodes.

Schematic diagram of a cell for voltammetric

measurements

SWASV

Results
Optimization of method
Optimization

pH

Supporting
electrolyte

Accumulation
potential

Accumulation
time

Frequency

Step
increment

Pulse
height

MWCNT
Modified
electrode

2.0

0.1 M KCl

0.00 V

60 seconds

100 Hz

2.0 mV

25.0 mV

SWASV of (a) unmodified MWCNT paste and (b) tetracarbonylmolybdenum(0) modified MWCNT paste
electrode.

Scheme 1 Proposed reaction mechanism of Cu2+ detection at the modified MWCNT

paste electrode

Electrochemical impedance spectroscopy studies

Electrode

Rct , ohm

Apparent rate constant

Unmodified MWCNT paste

electrodes

35.2

7.56 103 cm s1

Modified MWCNT paste electrodes

17.5

1.52 102 cm s1

The high kapp and low Rct values for the modified MWCNT paste is indicative of a faster electron
transfer process compared to the unmodified MWCNT paste electrode.

Calibration data

Linear range of 0.1 nM to 1.0 M Cu(II). R2 = 0.99138.

Limit of detection = 80 pM.

Good reproducibility with relative standard deviation of 3.6 % (n = 5).

Interference studies

Interference of most ions at 10 and 100-folds are negligible except from Pb(II).

This is presumably due to the formation of the intermetallic compound deposited on the
electrode surface.

Analytical application to wastewater samples

CONCLUSION

The tetracarbonylmolybdenum(0)/MWCNT paste electrode is successfully used for the

quantification of Cu(II) at trace level concentration.

The SWASV measurement shows wide linear working concentration range, lower limit
of detection, good reproducibility and high stability.

The electrode does not interfere by other metal ions except for Pb(II) ions.

The modified MWCNT paste electrodes was successfully used for the analysis of the
different water samples.