Environmental Photochemistry: Is Iron Oxide (Hematite) An Active Photocatalyst? A Comparative Study: A-Fe20,, Zno, Ti02
Environmental Photochemistry: Is Iron Oxide (Hematite) An Active Photocatalyst? A Comparative Study: A-Fe20,, Zno, Ti02
Environmental Photochemistry: Is Iron Oxide (Hematite) An Active Photocatalyst? A Comparative Study: A-Fe20,, Zno, Ti02
Summary
1. Introduction
2. Experimental details
2.1. Materials
Transparent o-FezOs colloids were prepared by the controlled hydro-
lysis of FeCl, which was followed by membrane dialysis until the residual
Cl- concentration was below 10m5 M. Particle diameters were found to be
between 3 and 20 nm. Details of the synthesis and characterization of this
catalyst have been described elsewhere 1121. Titanium dioxide (bandgap
energy, 3.2 eV) [ 131 was obtained from Degussa (P25); it had a BET surface
area of 50 + 15 m2 g-l and an average particle diameter of 30 nm. Zinc
oxide (bandgap energy, 3.4 eV) [13] was u.s.p. grade from Baker. Suspen-
sions were freshly prepared by sonication (< 60 s in Bransonic 5200 cleaning
bath). The concentrations employed resulted in an absorption of more
than 95% of the incident photons at 330 nm. Chloroacetic acid (MCB)
contained about 2 mol.% of Cl- as detected by ion chromatography (HPIC).
All chemicals were of reagent grade and used without further purification.
The water employed in all preparations was purified by a Mill&Q/R0 system
with an attached ORGANEX-Q unit (p > 18 MLn cm).
2.2. Apparatus
Illumination apparatus and actinometry have been described elsewhere
[ 141. Typically a volume of 2 ml suspension was illuminated with the
collimated beam of an Osram XBO 450 W lamp through a 300 nm UV
cut-off and an IR filter. The incident photon flux between 300 and 400 nm
was 1% 5 X lop3 M hu min-’ . Reaction temperatures were between 25 and
30 “C.
Hydrogen peroxide concentrations were determined by an enzymatic
and a polarographic method. Details have been described elsewhere 1143.
163
HPIC was performed with a Dionex 202Oi instrument (column, AS4A with
AG4 pre-column; eluant, 0.005 M Na,B&; flow rate, 2.0 ml min-’ ; detec-
tion, suppressed conductivity; sample volume, 50 ~1). Chloride concentra-
tions were also determined using a chloride sensitive electrode (Orion 9417).
In a typical illumination experiment 25 - 50 ~1 aliquots were taken, diluted
in 2500 ~1 of water (in the case of the Fez03 colloid, 0.5 mM NaOH was
used to precipitate the colloid) and subsequently analyzed by HPIC. The
degradation of volatile chlorinated hydrocarbons was monitored by gas
chromatography (HP 5880A Level Four instrument; column, 12 m HP-I,
isothermal at 35 “C; carrier gas, nitrogen at 1 ml min- ’ ; electron capture
detector (300 “C)). Typically, 10 ~1 of the headspace of the aqueous sample
solutions were injected.
to the experiments with the other oxides and were varied as follows: [CY-
Fe203] = (5 X 10p4)-(1 X 10m3) M; electron donor, [isopropanol] = 1 M or
[acetate] = 10 mM; [O,] = (2.3 X 10S4) - (1.3 X 10w3) M; pH 2 - 5; ionic
strength I = lo- 3 - lo-* M (KCl).
The different behavior of the three oxides can be explained if one
takes into account the redox potentials of the conduction band electrons
and of individual electron transfer reactions. While at pH 2 the redox potential
of the conduction band for bulk ZnO and Ti02 electrodes have been re-
ported to be Ecb = 0.0 V and Ecb = + 0.05 V respectively, the corresponding
value for cy-Fe203 is Ecb = +0.3 V [ 133. The redox potential of photo-
generated conduction band electrons in small particles may be somewhat
more negative (by about 0.1 V) than the redox potential of the conduction
band for bulk electrodes because of characteristic size effects [ 15, 161.
On the other hand, in homogeneous solution a value of E* = -0.15 V
(at pH 2) has been given for the reduction of oxygen [ 171:
e,,- + O2 + H+ + HO;
This value may be more positive when dioxygen is chemically bound to
the surface. It is obvious that the reduction of O2 by a conduction band
electron is most endothermic (AG” = -0.45 V or + 44 kJ mol-‘) in the case
of ar-Fe203. Hence, it is not surprising that the oxygen molecule is not
photoreduced on a-Fez03 particles.
3
0 Chloride
0
A Cl-Acetate
0 chloride A Cl-Acetate
A Cl-Acetate
0 Chloride
0 _ e
1 .oo
F OBO
+
2 0.60
!i
-5 0.40
+
i! 0.20 +
+
++
0 ++
60 120 IO
llluninatim Time / rnh
aRelative quantum yields calculated from pseudo-first-order rate constants given in Table 1 of ref. 4.
bThe authors of ref. 4, however, find equal yields of iodide oxidation in the presence and the absence of cr-Fe203.
168
Acknowledgment
References