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Diamond and Related Materials 12 (2003) 577–582

Efficiency study of perforated diamond electrodes for organic compounds

oxidation process
A.V. Diniza,b,*, N.G. Ferreirac, E.J. Corata, V.J. Trava-Airoldia
˜ Jose´ dos Campos, Brazil
Instituto Nacional de Pesquisas Espaciais, INPE, 12201-970, Sao
Departamento de Quımica ˜ Jose´ dos Campos, Brazil
– ITA-CTA, 12225-800, Sao
˜ de Materiais, AMRyCTA, 12228-904, Sao
Divisao ˜ Jose´ dos Campos, Brazil


The electrochemical oxidation of organic compound by bulk electrolysis has been analyzed for diamond electrodes used as
anode. Boron-doped diamond thin films were grown on titanium alloy substrates (Ti6Al4V) with a geometric area of 12.2 cm2
at 870 K and at 6.5=103 Pa. By using hot filament chemical vapor deposition technique and perforated and non-perforated
substrates, the films were grown in both sample sides. The electrodes were characterized from their electrochemical behavior as
a function of film quality, morphology and surface area, for boron concentrations of approximately 1018 ycm3 . The electrode
performance was determined by cyclic voltammetry measurements in acid and neutral solutions and the reversibility behavior of
the Fe(CN)3yy4y
6 at the Ti6Al4Vydiamond electrode were also studied. High performance liquid chromatography (HPLC) and
total organic carbon (TOC) techniques were used to study the oxidation products. These techniques are important to quantify the
different compounds in the oxidation process steps permitting to observe the diamond electrodes efficiency. The results have
shown a TOC decrease of approximately 85% and for HPLC it was observed almost complete phenol combustion to CO2.
Scanning electron microscopy and Raman scattering spectroscopy were also used for morphology and diamond quality evaluation,
䊚 2003 Elsevier Science B.V. All rights reserved.

Keywords: Phenol oxidation; Wastewater; Boron-doped diamond; Electrode

1. Introduction problems related to diamond film peeling became a goal

to be overcome. It usually occurs due to the generation
Diamond thin films have been widely used as elec- of high residual stresses in both films and substrate.
trodes in electrochemical studies due to the unique Thermal stresses are often high in diamond films as a
properties like chemical stability, large potential window result of high deposition temperatures and the difference
and mechanical resistance. Their applications embrace of the thermal expansion coefficient between diamond
the electroanalysis, electrosynthesis, fuel cell and the and Ti6Al4V w4x. Such stress component also represents
organic pollutant degradation in wastewater. The organic a challenge in this study. Some solutions for this problem
compound electrochemical oxidation efficiency strongly are being found, like the low deposition temperature
depends on the used anode material and diamond is conditions and stress relief by slow dropping tempera-
very interesting due to its superior properties w1,2x. ture, and have been considered for the film growth in
For diamond growing the use of titanium alloy sub- this work. A complete discussion of stress results for
strates is very desirable because its high specific diamond films grown on perforated and non-perforated
strength, fatigue resistance and low density if compared Ti6Al4V substrates, with a geometric area of 12.2 cm2,
with others available materials, or even with pure tita- is the subject of another work in progress. The use of
nium, in spite of the difficult in obtain good adhesion electrochemical process for wastewater treatment has
between this material and diamond films w3x. So, some demonstrated to be strategically a new technology by
*Corresponding author. Tel.: q55-12-3945-6903; fax: q55-12-
causing minor or no effects on the nature. In addition,
3945-6717. the large area obtained for polycrystalline CVD diamond
E-mail address: (A.V. Diniz). films associated with their high overpotentials for water

0925-9635/03/$ - see front matter 䊚 2003 Elsevier Science B.V. All rights reserved.
578 A.V. Diniz et al. / Diamond and Related Materials 12 (2003) 577–582

electrolysis has confirmed such electrodes as a promising experimental procedure are in previous work w11x. The
new material for organic compounds electrochemical samples of geometric area used for electrochemical
oxidation. Comninellis et al. w5–7x have discussed that analysis were 26 and 8.7 cm2 for perforated and non-
only reactions involving simple electron transfer pro- perforated diamondyTi6Al4V electrodes, respectively.
cesses are active on diamond electrodes. They also The characterizations of the film morphology and
proposed a generalized mechanism for the organic oxi- diamond quality were made by a LEO 440 scanning
dation in the potential region of O2 evolution. electronic microscopy system and by a Renishaw Micro-
In this work we have made electrochemical investi- scope 2000 micro-Raman scattering system, respectively.
gation for characterizing boron-doped diamondy The experimental procedure for TOC and HPLC meas-
Ti6Al4V electrodes on perforated and non-perforated urements will be explained in detail in Section 3.
substrates. Cyclic voltammetry in different electrolytes:
KCl, KNO3, Na2SO4, HCl, HNO3 and H2SO4, has been 3. Results and discussions
used to analyze the repeatability and reproducibility of
such electrodes when compared with our standard dia- 3.1. SEM and Raman
mondySi electrodes w8–10x. The reversibility behavior
was also studied by the Fe(CN)3yy4y6 redox system. SEM analysis for boron-doped diamond films on
Total organic carbon (TOC) and high performance liquid Ti6Al4V is depicted in Fig. 1. It is observed a poly-
chromatography (HPLC) techniques have used dia- crystalline film with predominant orientation (1 1 1) and
mondyTi6Al4V electrodes as anode for studying the (1 0 0). The films grew on the surface and on the border
phenol complete combustion. The results have shown a of the samples. The grains are very twinned, with
TOC decrease of approximately 85% and for HPLC it average size approximately 1 mm for 1.3-mm film
was observed almost complete phenol combustion to thickness. The thickness and the grain size are smaller
CO2. Emphasis for diamond growing on perforated in comparison with standard diamondySi electrodes w8x.
substrates has been done in order to increase the active This probably occurred due to the low deposition tem-
surface and to promote an easier electrolyte flux for perature w12x. Temperature as low as 600 8C is the best
wastewater treatment. The morphology and films quality value for diamond growth considering the benefits in
were also analyzed by SEM and Raman spectroscopy. terms of diamond quality and tow thermal stress com-
ponent w13x. It is important to remember that a TiC
2. Experimental interlayer is formed between the diamond films and the
Ti6Al4V. It is already known that low temperature
Depositions were performed using a medium sized results in low growth rate and small thickness of the
hot filament chemical vapor deposition reactor from a titanium carbide interlayer. These characteristics favor
1% CH4 vol. in H2 and an additional H2 line that passes the adhesion once the debonding occurs at the interface
through a bubbler containing B2O3 dissolved in metha- region between the TiC layer and the diamond film
nol, that correspond to acceptor concentrations of w14x.
approximately 1018 ycm3 w8x. Ti6Al4V 35=35=1.3 The Raman shift spectra of such films have evidenced
mm3 perforated and non-perforated samples have been narrow and splitted peaks at 1340ycm and a wide band
used. The perforation made by laser promotes a geo- centered at ;1550ycm. The displacement and the split-
metric area increase of approximately 30%. All samples ting of the diamond characteristic peak is attributed to
were ultrasonically prepared in a hexane bath and the the high residual stress in the film, observed for diamond
films were grown on both sides of the substrates. The films on Ti6Al4V. The positive shift was attributed to
temperature and pressure were 900"25 K and highly compressive stress w15,16x. The usual broad band
6.5=103 Pa, respectively. The reactor has a rotation at 1200ycm for boron-doped films is not evident yet,
mechanism for the substrate that provides better unifor- indicating a slightly doped diamond film.
mity to the film growth.
The electrodes were assembled over a Ti6Al4V foil 3.2. Cyclic voltammetry
base and electrical contact was made with a silver-based
paste. The group was isolated with silicone wax inside The electrochemical behavior has been studied in
a Teflon box. Cyclic voltammetry analyses were made order to analyze the electrode work potential window,
in a conventional three-electrodes (work electrode, reproducibility and reversibility behavior in comparison
counter electrode and reference electrode) in the single- to standard diamondySi electrodes in similar doping
compartment electrochemical cell by using a level. The electrochemical responses from non-perfora-
Microquımica potentiostat model MQPG-01. The solu- ted and perforated diamondyTi6Al4V in neutral solu-
tion was not stirred during the voltammetry experiments. tions have shown the same large potential window, as
Reference electrode and counter electrode were Agy expected. For all experiments the results are shown in
AgCl and a foil of platinum, respectively. Details of current density by considering the sample geometric
A.V. Diniz et al. / Diamond and Related Materials 12 (2003) 577–582 579

Fig. 1. Top view image from scanning electron microscopy for boron-doped diamond film grown on Ti6Al4V substrate.

surface area. The current density observed from the 3.3. Oxidation of organic compounds
curve of perforated diamond is higher than non-perfor-
The electrochemical oxidation of phenol at diamondy
ated diamond. It is probably due to the difference
Ti6Al4V electrode was performed from a 5 mmolyl
between the real and the geometric surface area for both
aqueous solution under galvanostatic conditions (30
mAycm2) for perforated and non-perforated diamondy
DiamondyTi6Al4V electrode performance was also
Ti6Al4V electrodes. Electrochemical measurements
evaluated by their electrochemical activity in acid and
were made in a conventional three-electrode cell by
neutral solutions. The results were compared with stan-
using a computer controlled EG&G PAR model 273A
dard diamondySi electrode in similar doping level. The
for keeping a constant current during the electrolysis.
current densities values of the anodic (Imax) and cathodic Diamond has been used as working electrode, AgyAgCl
(Imin) reactions, which correspond to oxygen and hydro- as a reference and Pt as a counter electrode. The TOC
gen evolution, have indicated a coherent response for of the solutions was monitored during the electrolysis
all electrodes analyzed when compared with diamondy using Shimadzu 5000 equipment. The phenol and main
Si electrode. In the acid solution, the cathodic current products as benzoquinone, hydroquinone and catechol
density is approximately 10 times larger and the anodic formed during its anodic oxidation were monitored
current density is similar to those in neutral solutions, during the electrolysis from the samples collected in
confirming the high sensitivity of the diamond surface determined time intervals and analyzed by HPLC. The
to hydrogen, in the form of Hq ions, as was observed chromatographic system consisted of a Shimadzu Model
by Deneuville et al. w17x. LC 10-AD pump, photodiode-array detector SPD-M
The reversibility for redox reactions in K4Fe(CN)6 10A, degasser DGU-14A and a system controller SCL-
solution was also studied for boron-doped diamondy 10A. Owing to the polarity of the phenolics reverse-
Ti6Al4V. The cyclic voltammetrics of Fe(CN)3yy4y 6 in phase elution was chosen and a Shim-Pack CLC-ODS
0.1 molyl KCl solution at perforated and non-perforated column was used. The mobile phase was 40% watery
samples are shown in Fig. 2. The data reported in this 60% acetonitrile at a flow rate of 0.80 sccm. In spite of
work are corrected by IR compensation. By using some they have been made calibration curves for the reagent
criteria to analyze the cathodic peak current and the and main formed products, in the used conditions, the
separation potential between the anodic and cathodic used method was not validated. In this sense, this
peaks, the results indicated that Fe(CN)3yy4y
6 couple is technique supplied only comparative results.
quasi-reversible at diamondyTi6Al4V, as it is at dia- The relative percentage of phenol converted in CO2
mondySi electrode. as a function of time is shown in Fig. 3 for the two
580 A.V. Diniz et al. / Diamond and Related Materials 12 (2003) 577–582

Fig. 2. Cyclic voltammetric behavior of the electrodes in 1 mM Ferrocyanidey0.1 M KCl. (a) non-perforated film; (b) perforated film.

samples studied. It was observed for perforated sample in the same conditions (current density, temperature and
a TOC relative percentage decrease of approximately pH), the relative percentage decreases only 60%. It is
85% with 5 h of experiment and such electrode seems important to emphasize that, in these measurements, the
to be more efficient than the non-perforated electrode. solution concentration is only 2 mmolyl. Iniesta et al.
In Ref. w18x, for electrolyses with diamond electrodes w19x have also found TOC value of approximately 16%

Fig. 3. Relative TOC percentage as a function of time for non-perforated and perforated diamondyTi6Al4V electrodes.
A.V. Diniz et al. / Diamond and Related Materials 12 (2003) 577–582 581

Fig. 4. Concentrations of phenol, benzoquinone and cathecol as a function of time from HPLC measurements for diamondyTi6Al4V electrode.

by using the solution concentration of 5 mmolyl, but have demonstrated higher efficiency than TiyRuO2 y
with a current density value 2 times larger than the TiO2 electrode.
current density used in our measurements.
The indication that phenol is directly oxidized at the 4. Conclusion
anode to CO2 has been confirmed by HPLC analysis
because the main intermediate formed during electrolysis Boron-doped diamond films were grown on perforated
present very low concentration values. The typical exam- and non-perforated Ti6Al4V substrates with good adhe-
ple of HPLC analyses of the solution during the oxida- sion. SEM and Raman scattering spectroscopy charac-
tion carried out at 30 mAycm2 and low phenol terized their quality and morphology indicating films
concentration (5 mmolyl) is shown in Fig. 4 for phenol, with small average size grain, highly stressed, slightly
benzoquinone, hydroquinone and catechol concentra- doped and with some quantity of sp2 carbon.
tions as a function of time. The phenol electroxidation The electrode electrochemical behavior demonstrated
efficiency can be obtained from the slope of linear similarity with the standard diamondySi electrodes in
curve, by the equation w20x: the same range of doping level. The electrochemical
properties, like large potential window, electrochemical
BK E activity in the different neutral and acid solutions and
C(t)sC(0)expC tF
reversibility behavior of the Fe(CN)3yy4y
6 at the elec-
trodes have demonstrated reproductive for the boron-
doping level studied.
by considering C the phenol concentration as a function TOC and HPLC results have evidenced that the use
of time, A the anode area in m2, V the electrolyte volume of such diamondyTi6Al4V electrode as anode for phenol
in m3 and KPh the phenol oxidation constant. The KPh oxidation is an attractive technology for promoting
value obtained from the result shown in Fig. 4 is almost complete oxidation to CO2, with small concen-
7.14=10y3 mys for diamondyTi6Al4V electrode. This tration of intermediates during the process and an
result is important when compared with similar experi- efficiency phenol two orders of magnitude higher than
ments made using TiyRuO2 yTiO2 electrode as anode TiyRuO2 yTiO2 electrode.
for phenol electroxidation process. Di Iglia et al. w20x
have obtained a phenol oxidation constant two orders Acknowledgments
of magnitude smaller for such electrodes using the
current density 5 times higher and the phenol concentra- We are very grateful to CNPq (process No. 381208y
tion 5 times smaller, so the diamondyTi6Al4V electrodes 97-4) and FAPESP (process No. 00y06756-0 for finan-
582 A.V. Diniz et al. / Diamond and Related Materials 12 (2003) 577–582

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