Cyclic voltam metric studies of the influence of surface chemistry on the electrochemical

behavior of granulated and powdered activated carbon samples in the presence of lead (II) ions
both in bulk solution and pre adsorbed on carbon were carried out.Variety in surface chemical
character was achieved through modification of carbon samples by heat treatment in vacuum,
ammonia and ammonia-oxygen atmospheres, as well as by oxidation in moist air and with
concentrated nitric acid. For the samples obtained, the surface area (BET), acid–base
neutralization capacities and sorption capacity towards Pb2+ ions were estimated. The states of
the deposited Pb species were assessed by means of FTIR and XPS spectra as well as cyclic
voltammetry. The importance of the surface chemistry of the carbon electrode material sare
discussed in terms of their electrochemical properties and the mechanism of adsorption
processes. The Cp-metal and hetero atom-metal interaction are dominant in amphoteric and basic
carbons, but in oxi-dized samples adsorption take place mainly by ion-exchange. Other forms of
adsorption, such as the formation metal hydroxide species, are also covered buy this paper.
Various forms of adsorbed lead species exhibit different electrochemical activities.

Different methods have been proposed for removing lead from contaminated water. Among
them, adsorption processes seem to be relatively effective and activated car-bon has been
suggested as adsorbent. Several researcher have demonstrated the ability of activated carbon to
remove Pb(II) from aqueous solutions on granular acti-vated carbon and other carbon adsorbents
in bath or fixed-bedadsorbers. Mostrecently, Radovicetal, 2001. Have reviewed the adsorption of
various ions, includ-inglead ,from aqueous solutions on carbon materials.

A commercial activated carbon (ROW 0.8 Supra—Norit, The Netherlands) was washed
(demineralized) with concentrated HF and HCl acids (ash content 0.2 wt%) and subsequently
modified by different meth-ods.Part of this carbon (indicated by AW parent sample) was used
without any additional processes.

1. Heating at 1173K under vacuum 102 Pa (HTV),

2. Heating in a stream of ammonia at1173K(HTA),

3. Heating in a stream of a1:1 oxygen–ammonia mixture at 673K (OPA),

4. oxidation with moist air at 673K (OWA),

5. oxidation with concentrated nitric acid at 353K (ONA).

After modification all samples were desorbed under vacuum at 473K (2h) and stored in
an argon atmosphere. The specific surface areas (SBET) of the carbon samples were determined
from low temperature (77 K) nitrogen isotherms obtained with ASAP-2000 instrument.
Additionally, the total oxygen and nitrogen con-tent in all samples was determined by elemental
analysis (accurate to 0.2%) on a CHNS-O model 1108 analyser (Carlo Erba, Milan).
The chemical properties of the modified carbon surface were determined by standard
neutralization titration with HCl, NaHCO3, Na2CO3, NaOH (0.1M in water) and NaOC2H5 (0.1M
in ethanol) according to the Boehm procedure [24,25]. Additionally, the pHs of carbon slurries in
0.1M NaCl (1g of carbon in 100 cm3 solution) were determined [26] .

FTIR spectra of the carbon samples were obtained using a Perkin Elmer FTIR Spectrum 2000
spectrome-ter. The activated carbon-KBr mixtures (1:300) were ground in an agate mortar,
desorbed under vacuum(10-2 Pa) and compressed in a hydraulic press.Thespec-tra were recorded
from 4000 to 400 cm-1 at a scan rate of 0.2 cm s-1 , and the number of interferograms at a
nominal resolution of 4 cm-1 was fixed at 25. Before the spectrum of a sample was recorded, the
background line was obtained arbitrarily and subtracted. The IR measurements applied here
(KBr-pellet technique) make it impossible to compare quantitatively the FTIR spectra obtained
for different carbons, but they do indicate which individual chemical structures may or may not
be present in the carbon [27].

The activated carbon samples were immersed and shaken in a nitrate solution in dark bottles for
48 h, after which the pH of the solutions and the Pb2+ concentration were determined, the latter
by colorimetric analysis using PAR (4-(2-pyridylazo) resorcinol monosodium salt hydrate) as
complexing agent [28] . After each experi-ment, the carbon materials were separated from the
solution by filtration, rinsed with doubly distilled water and then prepared for further analyses,
such as FTIR and XPS, or electrochemical measurements. Additionally, for several systems
(measurement of adsorption kinetics), cyclo voltammetric analysis of the Pb2+ ion concentration
using glassy carbon (3mm diameter) elec-trode was carried out.

XP spectra were obtained with an EscaLab 210 (V.G. Scientific Ltd.) Photoelectron spectrometer
using a nonmonochromatized AlKα radiation (1486.6 eV), the source being operated at 15 kV
and 34 mA. Prior to XPS measurement the powdered carbon samples were dried for 2 h at 100oC
(373 K). The vacuum in the analysis chamber was always better than 5x10-10 Pa. The high
resolution scans were performed over the 280–294, 395–407, 527–540 eV ranges (C1s, N1s and
O1s spectra, respectively) for samples before and after lead adsorption, and additionally, over the
135–144 eV range (Pb4f) after metal adsorption. In order to obtain an acceptable signal to noise
ratio the spectral region was scanned 20 times. After subtraction of the base line (Shirley-type),
curve fitting was performed using a non-linear least-squares algorithm and assuming a mixed
Gaussian/Lorentzian peak shape of variable proportion (mainly 0.3). This peakfitting was
repeated until an acceptable fit was obtained (error<5%). The positions of the deconvoluted
peaks (binding energy—BE) were determined from both literature data [29–31] and empirically
derived values.