Accepted Manuscript

Title: Advancing Fenton and photo-Fenton water treatment

through the catalyst design

Author: Alexander V. Vorontsov

PII: S0304-3894(18)30265-6
DOI: https://doi.org/10.1016/j.jhazmat.2018.04.033
Reference: HAZMAT 19316

To appear in: Journal of Hazardous Materials

Received date: 28-10-2017

Revised date: 13-4-2018
Accepted date: 16-4-2018

Please cite this article as: Vorontsov AV, Advancing Fenton and photo-Fenton
water treatment through the catalyst design, Journal of Hazardous Materials (2010),
https://doi.org/10.1016/j.jhazmat.2018.04.033

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Advancing Fenton and photo-Fenton water treatment through the
catalyst design

Alexander V. Vorontsov*

Altai State University, pr. Lenina 61a, Barnaul 656049, Russia

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*e-mail: a-voronts@yandex.ru

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*ORCID: 0000-0002-2791-3278

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Revision 2

Submitted to: Journal of Hazardous Materials U

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Special Issue: Photocatalysis: Future Trend
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2018
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Graphical abstract
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Rate constants Mechanism

measurements switching causes
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Fenton Family of and calculations and new steps

Reactions for all steps introduction
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FeII/FeIII/FeIV Research
directions
Classical Heteroge-
Fenton-like Design of
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Fenton neous Fenton

and photo- Mass transport complexes and
and photo- and photo-
Fenton-like enhancement heterogeneous
Fenton Fenton catalysts

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Highlights

 Mechanisms of Fenton and photo-Fenton processes are considered

 Obstacles for application of (photo-)Fenton(-like) reactions are given
 Directions of future basic and applied research on Fenton reactions are stated
 Heterogeneous photo-Fenton systems activated by solar light are most stable

ABSTRACT

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The review is devoted to modern Fenton, photo-Fenton, as well as Fenton-like and photo-
Fenton-like reactions with participation of iron species in liquid phase and as heterogeneous

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catalysts. Mechanisms of these reactions were considered that include hydroxyl radical and

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oxoferryl species as the reactive intermediates. The barriers in the way of application of these
reactions to wastewater treatment were discussed. The following fundamental problems need

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further research efforts: inclusion of more mechanism steps and quantum calculations of all rate
constants lacking in the literature, checking the outer sphere electron transfer contribution,
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determination of the causes for the key changes in the homogeneous Fenton reaction mechanism
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with a change in the reagents concentration. The key advances for Fenton reactions
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implementation for the water treatment are related to tremendous hydrodynamical effects on the
catalytic activity, design of ligands for high rate and completeness of mineralization in short
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time, and design of highly active heterogeneous catalysts. While both homogeneous and
heterogeneous Fenton and photo-Fenton systems are open for further improvements,
heterogeneous photo-Fenton systems are most promising for practical applications because of the
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inherent higher catalyst stability. Modern methods of quantum chemistry are expected to play a
continuously increasing role in development of such catalysts.
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Keywords: Fenton-like; photo-Fenton-like; heterogeneous Fenton; DFT; ligands; mechanism

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1. Introduction

Elimination of water pollutants is a very important stage of modern industrial chemical

production, agriculture and municipal water cycle. Conventionally used microbiological water
treatment has limited applicability because many pollutants are powerful biocides. Compared to
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other advanced oxidation technologies such as UVC light photolysis in combination with strong
oxidants, Fenton and photo-Fenton reactions provide significant advantages. Energy utilization is
reduced due to the dark usage of cheap reagent hydrogen peroxide H2O2 in Fenton reaction. Free
solar radiation can be utilized to carry out the photochemical stages of the photo-Fenton reaction
so that complete mineralization of organic compounds is possible in a short period of time [1].

Fenton reaction was reported for the first time by H. J. Fenton in 1894. He observed partial
oxidation of tartaric acid into dihydroxy maleic acid in the presence of iron (II) and hydrogen
peroxide [2]. Since then, Fenton reaction has been used to treat water contaminated with a

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variety of organic and biological pollutants and in organic synthesis. Such reactions as

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epoxidation, hydroxylation, dehydrogenation, and oxygenation proceed under the action of
Fenton reagent. The scope of the present review is limited to the application of Fenton and

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photo-Fenton reactions for unselective oxidation of water pollutants in order to eventually obtain

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water free of any organic compounds. The Fenton and especially photo-Fenton reaction have
been proven to be efficient in achieving this goal [3].

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However, the standard Fenton and photo-Fenton reactions involving inorganic FeII salts and
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H2O2 have a number of problems that prevent their widespread application to waste water
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treatment. Main problems are incomplete pollutants mineralization in Fenton reaction, narrow
pH range for obtaining the highest rate, waste of H2O2 for molecular oxygen production, low
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degradation rate for some chemicals and instability of the dissolved iron catalyst [4].
Advancements in application of Fenton and photo-Fenton reactions to water treatment are
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directly related to solving these problems. An empirical approach consisting in optimization of

reaction parameters such as concentration of reagents can help to overcome some of the
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problems to some extent [3]. A much larger breakthrough is possible via designing or choosing
Fenton and photo-Fenton reaction catalysts on the basis of deep theoretical grounds. Careful
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catalyst design requires deep knowledge of the reaction mechanism for overcoming the rate and
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stability limiting stages. It is shown in the following sections that complete mechanism is still
not known even for the simplest Fenton reaction, and reaction models for the reaction rate
prediction have to be based on empirical relations to a large extent. Moreover, no active research
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is taking place to obtain a complete theoretical model with reliable data on all elementary stages
despite all the modern research capabilities available. This review considers the full knowledge
on the mechanism of Fenton and photo-Fenton reactions and properties of catalysts that are
related to a high near-neutral pH activity, a low hydrogen peroxide waste, the sufficient catalyst
stability and the high extent of mineralization of organic compounds.

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Several reviews have been published recently on Fenton, photo-Fenton and Fenton-like reactions
[3,5–9]. All the reviews emphasize good prospects of these advanced oxidation processes for
wastewater treatment. However, the problems and questions remaining in the field are usually
not given in the form ready for the research objectives. The studies mostly repeat the same
experiments on the effects of operational parameters on the reaction with some variation in
pollutants and catalysts. However, fundamental questions on the rate constants of elementary
stages of even the simplest Fenton process remain unanswered. Moreover, these fundamental
questions are even not articulated at all. The present review is not intended to be a simplified

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educational introduction in the field that can be found in excellent previous reviews [5,6].

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2. Mechanism of Fenton and photo-Fenton reaction without complexing

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agents

Mechanism of a chemical reaction is understood in the present and further sections as a set of

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elementary steps. Dynamics of each elementary step is not considered in details bigger than rate
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constant, activation energy Ea and/or free energy of activation G≠. Instead, we focus on the full
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mechanism and its key steps determining the overall reaction rate called rate limiting steps.
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Development of knowledge about the mechanisms of Fenton and photo-Fenton reactions has
been taking place since the first report by Haber and Weiss in 1932 who suggested hydroxyl
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radical as reactive intermediate [10], continued with suggestion of ferryl as intermediate [11] and
is said to be far from finishing nowadays [12,13]. Here we would not go into deep historical
development of the mechanism because reviews on this matter are already available [14,15].
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Reactants of classical Fenton and photo-Fenton reaction are: inorganic salts of iron (II) dissolved
in water which convert into aquacomplexes [Fe(H2O)6]2+ designated as FeIIaq upon dissolution;
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dissolved hydrogen peroxide (H2O2), organic compound to be degraded by the reactions (RH);
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and, in the case of the photo-Fenton reaction, quanta of light designated h.
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Reactive intermediates (RI) of Fenton and photo-Fenton reactions comprise short-living species
of radical or non-radical nature including the following: very active species – hydroxyl radicals
(OH˙), oxoferryl species (FeIV=O); reactive oxygen species (ROS) – hydroperoxyl radical
(HO2˙), superoxide radical (O2-˙); organic radicals – alkyl (R˙), peroxyl (RO2˙); and compounds
unstable in aqueous solution like tetroxides (ROOOOR).

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The mechanism of Fenton and photo-Fenton reactions involve several groups of steps related to
their role in these free radical chain reactions: (I) production of very active oxygen-containing
species that initiate the oxidation; (II) transformation of very active oxygen-containing species
into other ROS; (III) reactions of oxygen species with organic compounds and their further
transformations; (IV) termination of reactive intermediates. The most important steps of these
groups of steps are given in Scheme 1 for oxidation of an organic compound RH.

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(I) Chain initiation steps - generation of very active species:

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k
FeIIaq + H2O2 
1
 FeIIIOHaq + OH˙, (1)

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k2
FeIIaq + H2O2   FeIV=Oaq + H2O, (2)

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h
FeIII(OH)aq  FeIIaq + OH˙. (3)

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(II) Chain propagation steps involving only ROS:
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k
FeIIIOHaq + H2O2 
4
 FeIIaq + HO2˙ + H2O, (4)
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K5

FeIIIOHaq + H2O2  FeIIIOH(OOH)aq + H+, (5)
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k
FeIIIOH(OOH)aq 
6
 FeIIaq + OH- + HO2˙, (6)
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k
FeIIIOHaq + HO2˙ 
7
 FeIIaq + O2 + H2O, (7)

k
FeIIIOHaq + O2-˙   FeIIaq + O2 + OH-,
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(8)
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k
H2O2 + OH˙ 
9
 H2O + HO2˙, (9)

k
HO2- + OH˙ 
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10
HO2˙ + OH-, (10)

k
HO2˙ + H2O2 
11
O2 + H2O + OH˙, (11)

k
O2-˙ + H2O2 
12
O2 + OH- + OH˙, (12)

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(III) Chain transfer and termination steps involving organic compounds:

k
RH + OH˙ 
13
R˙ + H2O, (13)

k
FeIV=Oaq + RH 
14
FeIIaq + ROH, (14)

k
R˙ + O2 
15
RO2˙, (15)

k

16
FeIIaq + RO2˙ 
K16

FeIIIOOR   FeIIIaq + RO2-, (16)

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k
RO2˙ 
17
R1R2CH2CH2 + HO2˙, (17)

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k
RO2˙ + RO2˙ 
18
ROOOOR, (18)

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k
ROOOOR 
19
R1OH + R2CHO + R3CO + O2, (19)

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(IV) Chain termination steps involving ROS:
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k
FeIIaq + OH˙ 
20
FeIIIOHaq, (20)
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k
FeIIaq + HO2˙ 
21
FeIIIaq + HO2-, (21)
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k
FeIIaq + O2-˙ + H+ 
22
FeIIIaq + HO2-, (22)

k
FeIIIOHaq + HO2˙ 
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23
FeIIaq + H2O + O2, (23)

k
FeIIIaq + O2˙- 
24
FeIIaq + O2, (24)
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k
FeIV=Oaq + H2O2 
25
FeIIaq + O2 + H2O, (25)

k
FeIV=Oaq + FeIIaq 
26
2FeIIIOHaq, (26)
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k
OH˙ + OH˙ 
27
H2O2, (27)

k
HO2˙ + OH˙ 
28
H2O + O2, (28)

k
HO2˙ + HO2˙ 
29
H2O2 + O2, (29)

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Scheme 1. Major steps of the mechanism of classical Fenton and photo-Fenton reactions.

Table 1 lists available rate constants and activation energies for the steps of Fenton and photo-
Fenton reaction. Various versions of the mechanism of Fenton and photo-Fenton reactions and
their important fragments are often given in the literature [1,3,4,16–20]. The literature
mechanisms often include steps only related to hydroxyl radical initiated oxidation and often do
not include steps related to ferryl driven oxidation and related reactions. This is possibly due to a

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low contribution of oxoferryl species in the standard conditions of the classical Fenton reagent.

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Recent investigations on iron chemistry in the presence of ozone and hydrogen peroxide and in
pulse radiolysis collected evidences on generation of oxoferryl iron complexes (H2O)5FeIV=O in

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conditions of Fenton reaction. Pignatello et al. [4] provided evidence for the contribution of

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ferryl complexes to photo-Fenton reaction using isotope effect in cyclohexane oxidation.
Addition of strong OH˙ scavenger and weak oxoferryl scavenger t-butanol did not stop the

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reaction, increased isotope effect up to 1.4 but has no influence on isotope effect for H2O2
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photolysis initiated oxidation and stopped this reaction. Flash photolysis showed broad
absorbance of some transient species with lifetime of about 100 ns that species can be attributed
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to oxoferryl complexes. Kremer [21] argued that FeO2+ is the key RI in Fenton reaction at low
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concentration of Fe2+ of 10-4 M and H2O2 of 10-5 – 10-3 M and FeO2+ reacts with Fe3+ to give
another RI, a dimer FeOFe5+. Further, there are arguments that oxoferryl species can produce the
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same products and same adduct with DMPO as hydroxyl radical [22]. Therefore, RI for the low
concentrations range that is of special relevance for elimination of trace water pollutants are the
subject of debate.
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The mechanism outlined in steps (1) – (29) do not pretend to be complete and reflect all possible
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steps of Fenton and photo-Fenton reaction in aqueous solutions of inorganic iron salts. It
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however includes both hydroxyl radical and oxoferryl as reactive intermediates and their parallel
chemistry related to hydrogen peroxide conversion into molecular oxygen, related propagation
and termination steps. It is important to include reactions with oxygen as they give very
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important contribution to Fenton and photo-Fenton chemistry, and their absence caused very
serious deviations of the results of modeling from experimental data [23]. However, many
related rate constants are not yet known and there is a need to measure them or calculate using
high precision methods of quantum chemistry. Electron transfer reactions with participation of
RI and organic compounds are also important steps of Fenton and photo-Fenton reactions [24]
and their relative role for many organic substrates is unknown.
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As it was outlined in Introduction, utilization of traditional Fenton and photo-Fenton systems for
water purification has serious barriers. Precipitation of FeIII at pH above 3 sets the limitation on
the pH needed for obtaining significant rate of pollutants degradation and stability of Fenton
reagent to pH around 3.5. Utilization of low concentration of FeII of < 1 mM allows increasing
pH value to 6 without iron hydroxides precipitation [25]. However, catalytic stability of such
system is limited to wastewaters that do not capture iron into inactive complexes or adsorbates.
Usual inorganic coordinating ions such as halides, sulfate, selenate, phosphates as well as
organic acids can inhibit production of the most active oxidant species or scavenge them

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[18,26,27].

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The rate of Fenton oxidation of organic compounds is limited by steps (4) – (8) responsible for
regeneration of FeIIaq. Complete mineralization of organic compounds is difficult to achieve in

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Fenton system due to the formation of stable iron complexes like oxalates and formates with

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partial oxidation products. These complexes can be destroyed efficiently via UV or visible light
irradiation in the photo-Fenton systems [24]. The photochemistry of such steps is considered in

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section 3 since such organic iron complexes can be actually good catalysts for Fenton- and
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photo-Fenton-like systems.
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Table 1. Rate and equilibrium constants for the steps of Fenton and photo-Fenton reactions
according to Scheme 1.
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Step number Rate constant or equilibrium constant Activation energy

-1 -1 -1 -1
1 40 to 80 M s [3,8,28], 586 M s for 42±1 kJ/mol [4]
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FeII(OH)2 at pH > 4 [4] G≠ = 23 kJ/mol [29]

2 < 0.7 M-1s-1 [28], ~103 M-1s-1 [12] G≠ = 31 kJ/mol, reverse
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reaction 35 kJ/mol [30]

3 Depends on light flux
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4 9.1·10-7 M-1s-1 [3], 0.01 M-1s-1 [18], 0.02 M-1s-1

[31], 0.001 – 0.01 [9]
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5 (2±0.5)·10-4 [4]
6 0.0027 s-1 [4] for Fe(O2H)2+ and Fe(OH)(O2H)+
7 1·106 M-1s-1 [18], 2.0·103 M-1s-1 for Fe3+ [1]
8 5·107 M-1s-1 for Fe3+ [4]
9 (1.7 – 4.5)·107 M-1s-1 [3,8,18]
10 7.5·109 M-1s-1 [1], (5.6 – 8.3)·109 M-1s-1 [32]

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11 0.5 M-1s-1 [18], 3 M-1s-1 [4]
12 16 M-1s-1 [33], 0.13 M-1s-1 [34]
13 107 – 1010 M-1s-1 [17]
14 3.1 – 1.26·105 M-1s-1 [7]
15 109 M-1s-1 [4], 107 – 109 M-1s-1 [35]
16 (1.2 – 5.0)·106 M-1s-1 [20,36]
17 400 – 2600 s-1 [36], 3 – 105 s-1 [35]
18 107 M-1s-1 [33]
19 Not available

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20 (2.5 – 5)·108 M-1s-1 [3,8,17]

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21 (0.72 – 1.5)·106 M-1s-1 [3,8] G≠ = 41.0±0.4 kJ/mol [37]
22 1·107 M-1s-1 [8] G≠ = 35.8±0.3 kJ/mol [37]

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23 (0.33 – 2.1)·106 M-1s-1 [3] 2·103 M-1s-1

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24 5·107 M-1s-1
25 (1.0±0.1)·104 M-1s-1 [38]
26
27
(1.4±0.2)·105 M-1s-1 [38]
(5 – 8)·109 M-1s-1 [3,18] U Ea = 8 kJ/mol [32]
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28 (0.66 - 1.4)·1010 M-1s-1 [1,3,32]
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29 (0.8 – 2.2)·106 M-1s-1 [3,18], (8.3±0.7)·105 M-
1 -1
s [8,39]
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Besides irreversible steps of Fenton and photo-Fenton reactions outlined in Scheme 1, a number
of aqueous phase equilibria are important for the course of these reactions. The most important
equilibria are related to Fe(II) and Fe(III) aquacomplexes. [FeII(H2O)6] is relatively stable to
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hydrolysis at pH up to 7 - 8 [9]. Care should be taken when equilibria constants are taken from
literature. For example, equilibrium constant for the second stage of FeIIaq hydrolysis in equation
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(31) turns out to be higher than that for the first stage in equation (30) if equilibrium constants
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from [4] are taken.

K

30
[FeII(H2O)6]2+ + H2O   [FeII(H2O)5OH]+ + H3O+, (30)
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K30 = 7.7·10-6 (dimensionless) [4],

K

31
[FeII(H2O)5OH]+ + H2O   [FeII(H2O)5(OH)2] + H3O+, (31)

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Precipitation of ferric species is the leading cause for low efficiency of classical Fenton and
photo-Fenton systems at pH above 3 -4 [9]. The related equilibria are shown in equations (32)
and (33). Attention should be paid to the correct dimensionality of the equilibria constants as in
the literature, constants are often reported that have dimensions incompatible with corresponding
equations [4,27].

K

32
[FeIII(H2O)6]3+ + H2O   [FeIII(H2O)5OH]2+ + H3O+, (32)

K32 = 2.34·10-3 [34],

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K

33
[FeIII(H2O)5OH]2+ + H2O   [FeIII(H2O)5(OH)2]+ + H3O+, (33)

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K33 = 2.00·10-3 [34].

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Further important equilibria include interaction of FeIIIaq with hydrogen peroxide. The reaction of
[FeIII(OH)(H2O)5]2+ with H2O2 is shown in equation (5) of Scheme 1. The equilibrium constant

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for this reaction is reported in Table 1. Interactions of H2O2 with other FeIIIaq species are shown
in the equations (34) and (35). Additionally, dimerization and polycondensation of FeIIIaq into
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nanoparticles are important for the aqueous phase chemistry since they give rise to precipitation
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at pH above 3.
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K

34
[FeIII(H2O)6]3+ + H2O2   [FeIII(H2O)5(HO2)]2+ + H3O+, (34)
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K34 = (3 - 9)·10-3,

K

35
[FeIII(OH)2(H2O)4]+ + H2O2   [FeIII(OH)2(H2O)3(HO2)]+ + H3O+, (35)
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K = 2·10-4 [40].
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Acid-base equilibria of water, hydrogen peroxide and ROS finalize the set of most important
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reversible reactions that should be and can be taken into account in analysis of kinetics of Fenton
and photo-Fenton reactions.
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K

36
H2O + H2O   H3O+ + OH-, (36)

K36 = 1.80·10-16,

K

37
H2O2 + H2O   HO2- + H3O+, (37)

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K37 = 2.86·10-14 [1],

K

HO2˙ + H2O 
38
 O2-˙ + H3O+, (38)

K38 = 2.84·10-7 [4].

Rate limiting steps in Fenton and photo-Fenton reactions are associated with steps (1), (2) and
(3) of production of reactive intermediates - hydroxyl radicals and oxoferryl species – that
initiate oxidation of dissolved organic species by converting them into alkyl radicals. Further

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transformations of alkyl radicals in aerated solutions are reactions with dissolved oxygen with
production of peroxyl radicals. If initial ferrous concentration is much lower than concentration

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of hydrogen peroxide, regeneration of ferrous ions from ferric ions limits the production of RI.

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Modifications of Fenton and photo-Fenton process can accelerate the rate of RI production,

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catalyst regeneration and widen the suitable pH range. An interesting option is the addition of
complexing agents.

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3. Mechanism of Fenton and photo-Fenton reaction in the presence of organic
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complexing agents
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This section considers changes in mechanism of Fenton and photo-Fenton reactions introduced
upon additions of organic chelating agents. These reactions are often called Fenton-like and
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photo-Fenton-like if organic chelating agents are added deliberately to the reaction mixture. The
negative effects caused by additions of inorganic complexing agents like chlorides, sulfate or
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phosphate were considered shortly in section 2. There are five marked effects occurring as a
result of introduction of organic complexing agents. The first effect is related to significant
acceleration of RI production in the step described in equation (1). This accelerating effect
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depends significantly on the ligands, aqueous media acidity and concentration of hydrogen
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peroxide. For the case of oxalate ligand, hydroxyl radical production is accelerated according to
the equation (39).
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k
[FeII(C2O4)] + H2O2 
39
[FeIII(C2O4)] + OH- + OH˙, (39)

k44 = 1·104 M-1s-1 [4].

The second effect of organic complexing agents is the change in predominant very reactive
oxygen species produced. This is caused by different acceleration of steps in equations (1) and

11
(2) of Scheme 1. For example, Fenton reaction in the presence of diethylenetriaminepentaacetate
(DETAPAC, DTPA) produces mostly OH˙ radicals as reactive intermediate while in the
presence of ethylenediaminetetraacetate (EDTA), oxoferryl FeIV=O is the dominant RI as
equation (40) demonstrates [41,42]. However, at high concentration of H2O2 (>1 mM), OH˙ is
the dominant RI for both iron (II) complexes.

k
[FeIIEDTA] + H2O2 
40
[OFeIVEDTA)] + H2O, (40)

k40 = 1.75·104 M-1s-1 [4].

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The reaction of oxoferryl species with alkanes involves two steps, hydrogen atom abstraction

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and rebound of hydroxyl group to the alkyl radical formed. There is a possibility of concerted

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mechanism of alkanes hydroxylation which is however energetically unfavorable compared to
the rebound mechanism [43].

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Another important effect of complexing agents consists in limiting Fe III precipitation at near

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neutral pH. Thus, Fenton-like water treatment can be performed without acidification.
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In some cases, complexing agents are added in order to reduce FeIIIaq into FeIIaq. This is done for
the case of using additions of 1,2-dihydroxybenzenes which are oxidized into corresponding
A
semiquinone and quinine [44]. Various colored molecules and dyes can also participate in FeIII
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photoreduction via supplying electrons from their photo-excited species as the following
equations illustrate.
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h
DH  DH*, (41)
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k
FeIII + DH* 
42
FeII + D˙ + H+. (42)

N,N-dimethyl aniline, rhodamine B and malachite green promoted photoreduction of iron(III) to

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iron(II) and consequently decomposition of hydrogen peroxide [45]. Principal differences

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happen in the mechanism of photo-Fenton reaction as a result of forming complexes with

organic ligand(s). Absorption of light quantum results in ligand to metal charge transfer (LMCT)
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followed by expulsion of the oxidized ligand and its further transformations [8,46].

h
FeIIIL2  FeIIL + L+˙, (43)

k
FeIII + L+˙ 
44
FeII + L2+, (44)

12
Absorption of light by iron (III) carboxylates results in decarboxylation of a ligand with
evolution of carbon dioxide. Photolysis of iron (III) oxalate follows reactions (45) – (48).

h
[FeIII(C2O4)3]3-  [FeII(C2O4)2]2- + C2O4˙-, (45)

k
FeIII + C2O4˙- 
46
FeII + 2CO2, (46)

k
C2O4˙- 
47
CO2 + CO2˙-, k47 = 2·106 s-1 [4], (47)

T
k
CO2˙- + O2 
48
CO2 + O2˙-. (48)

IP
Protonation of O2˙- in aqueous solution produces its conjugated acid. As a result, hydroperoxyl
radicals are produced and FeIII is converted into FeII with quantum yield similar to 100%.

R
Consequently, photo-Fenton degradation of organic compounds in the presence of iron (III)

SC
oxalate is very fast. Iron complexes with monocarboxylated acids upon LMCT photoexcitation
produce alkyl radicals and regenerate FeII.

h
FeIII(RCOO)2+  FeIIaq + R˙ + CO2. U (49)
N
A
This step allows driving the water purification up to complete mineralization of dissolved
organic compounds with photo-Fenton process. However, as the organic acids transform into
M

CO2 and leave the aqueous solution, iron stabilization disappear and iron (III) species are
precipitated if the pH of the initial solution was not acidic enough [46]. Such a precipitation
ED

retards the process of complete mineralization. One solution to this problem can be to subject the
photo-Fenton treated water to final biological treatment. An alternative approach is to use
PT

heterogeneous catalysts for the Fenton reaction that are precipitated from the beginning of the
reaction.
E
CC

4. Basic notions about Fenton and Photo-Fenton reaction mechanism over

heterogeneous catalysts
A

Iron (II) and iron (III) cations of heterogeneous catalysts are involved in three types of reactions
in the course of Fenton and photo-Fenton processes: homogeneous chemistry with iron leaked
from the solid surface; interface chemistry with iron cations residing in the surface of solid
catalyst analogous to homogeneous Fenton and photo-Fenton chemistry; interface chemistry
involving photogenerated charge carriers in semiconductor solids [7].

13
Leaking of iron is difficult to avoid because organic acids are usually formed in oxidation of
water pollutants and surface iron is extracted into solution by complexation with acids. The
leaked iron behaves in the same manner as in regular Fenton and photo-Fenton reactions and
provides the highest performance at pH around 3.

Interface Fenton and photo-Fenton chemistry is the desirable and attractive mode of action of
heterogeneous iron-containing catalysts. Both hydroxyl radicals and oxoferryl reactive
intermediates are formed in different proportions on the catalyst surface depending on the
catalyst and conditions of carrying out the reaction. The rate of interface Fenton reaction

T
increases as the surface area of catalyst increases [47] and porosity increases [31,48].

IP
Band gap excitation of solid semiconductor catalysts produces photogenerated electrons and

R
holes that can reduce and oxidize adsorbed species. This can result in production of additional

SC
organic radicals and hydroxyl radicals according to the following equations [8]:

h
FexOy  h+ + e-, (50)

h+ + RH 
k
R˙ + H+, U
N
51
(51)
A
k
e- + H2O2 
52
OH- + OH˙, (52)
M

h
FexOy–OH  FexOy + OH˙, (53)
ED

K

54
FexOy + H2O2   FexOy-O2H + H+, (54)

h
FexOy-O2H  FeIV=O + OH-. (55)
PT

Generation of reactive intermediates, hydroxyl radicals and high-valent iron oxospecies, limit the
E

rate of heterogeneous photo-Fenton reaction. Careful choice and deliberate design of

CC

heterogeneous catalysts is considered as the solution for the problem of low activity of
heterogeneous Fenton systems. A recent report on a very high activity of FeOCl nanosheet
Fenton catalyst in a wide pH range confirms the excellent prospects of heterogeneous systems
A

[49].

5. Remaining questions on the mechanism of Fenton and photo-Fenton

reactions

14
Advancement of fundamental understanding of the Fenton processes is important for the
development of water treatment methods and technologies. The nature of the key steps (1) and
(2) of the Fenton reaction mechanism remains the subject of debates. It is assumed that these
stages proceed exceptionally as inner sphere electron transfer. There are arguments, but mostly
speculative, that hydroxyl radical production cannot proceed via outer sphere electron transfer
[2]. Quantum chemical calculations of the relative rates of inner sphere and outer sphere
alternatives should shed light on their contribution. The possibility of contribution of outer
sphere electron transfer to reaction (1) is indirectly supported by literature examples of parallel

T
inner sphere and outer sphere electron transfer reactions between iron complexes and dissolved

IP
molecules [50].

During the last two decades, an extensive computational investigation has been undertaken by

R
several research groups on inner sphere reactions between FeIIaq and H2O2. Using FeII(H2O)5 and

SC
attached H2O2 as the starting species and ab initio DFT molecular dynamics, formation of
(H2O)5FeIIIOH and OH˙ was observed but OH˙ abstracts hydrogen atom from one of the

U
coordinated water molecules in the iron complex within few picoseconds to result eventually in
(H2O)5FeIV=O [51,52] as the equations (56) – (58) demonstrate.
N
A

 [(H2O)5FeII(H2O2)]2+ + H2O,
[(H2O)6FeII]2+ + H2O2 
 (56)
M

[(H2O)5FeII(H2O2)]2+ 
 [(H2O)4FeIV(OH)2]2+(H2O), (57)
ED

[(H2O)4FeIV(OH)2]2+ 
 [(H2O)5FeIV=O]2+. (58)

This contradicts experimental results on hydroxyl radical or another RI of Fenton reaction

PT

lifetime of nanoseconds. The problem with such computer simulations can be the very
concentrated FeIIaq solution of 1.7 M that was used in modeling. Also the validity of employed
E

DFT methods for reactions under investigation was not tested and need to be compared with
CC

experimental thermodynamics and kinetics data.

The high yields of diferryl species [Cl4FeIIClFeIV=O]- and [Cl5FeIIIClFeIV=O]- were detected by
A

mass-spectrometry in microjet reaction between FeCl2 in concentration 10 M and gaseous H2O2

in concentration 0.3 ppm [12]. Monoferryl species were not detected. The diferryl species are
quenched by additions of t-BuOH. Much higher (in ~103) rate of reaction between FeIIaq and
H2O2 was observed in special conditions of hydrodynamics of interfaces between microjets and
gaseous H2O2. Applicability of such conditions of gas-liquid interfacial chemistry to water
treatment needs to be investigated. If such high rate of pollutants abatement could be realized in
15
water treatment, it would be a breakthrough in AOTs. It is possible that very efficient mixing of
reagents allows fast access of H2O2 to the core of FeIIaq hydrated species, a condition not realized
in traditional “slow” mixing in homogeneous chemistry. An adequate explanation of the striking
difference of the reaction rate constants of Fenton reagent depending on hydrodynamic
conditions is absent in the literature.

Further questions concern the change in Fenton reaction mechanism upon change in ferrous and
hydrogen peroxide species concentration. While oxoferryl species are operative at low
concentrations, hydroxyl radicals are the key RI at high concentration [53]. An explanation of

T
this change in mechanism is unavailable currently.

R IP
6. Organic ligands important for Fenton and photo-Fenton reactions

SC
Many organic ligands containing several carboxyl groups were demonstrated to produce high

U
rates of degradation in Fenton and photo-Fenton systems at near neutral pH . Such systems are
usually called Fenton-like and photo-Fenton-like reactions. Nitrogen containing ligands can also
N
function in Fenton-like reagents and form active oxoferryl and Fe(IV) dihydroxo complexes
A
driving oxidation of alkens [54]. Cyclic tetradentate N4 ligands can be classified as heme-like
M

and nonheme according to their chemical structure. Prominent heme-like ligands are
phthalocianines and porphines. A prominent nonheme cyclic ligand is 1,4,8,11-tetramethyl-
1,4,8,11-tetraazacyclotetradecane also called tetramethylcyclam (TMC). FeII(TMC)L with
ED

different axial ligands was demonstrated experimentally and computationally to be easily

converted by reaction with H2O2 into the corresponding oxoferryl complex that has G≠ = 23 –
PT

32 kcal/mol in hydrogen abstraction from methane [55–57].

The third type of organic ligands contain multiple phosphonic acid groups. Aminophosphonic
E

acids are used as stabilizers of hydrogen peroxide solutions. Four ligands –

CC

ethylenediaminetetrakis (methylenephosphonic acid) (EDTMP), hexamethylenediaminetetrakis

(methylenephosphonic acid) (HMDTMP), diethylenetriaminepentakis (methylenephosphonic
A

acid) (DETAPMP), and aminotris (methylenephosphonic acid) (NTP) – that are analogs of the
EDTA, HMDTA, DETAPAC and NTA were used in iron (II) complexes as Fenton reagent
catalysts [58]. It turned out that the iron (II) complexes with these methylenephosphonic acids
reacted with H2O2 at pH 6 to 7 very fast and the second-order rate constants were in the range
from 1·104 to 2·105 M-1s-1. These rate constants are about an order of magnitude larger than for

16
the EDTA, DETAPA and NTA. However, the reactivity of these iron complexes in degradation
of water pollutants has not been studied.

The majority of studies on water treatment with Fenton-like and photo-Fenton-like reactions
utilize polycarboxylate ligands [22]. Table 2 demonstrate structural formulas of such ligands.
FeIII(Cit)2 is one of the prominent Fenton-like catalysts. It can produce about seven-fold higher
concentration of hydroxyl radicals for an extended period of time compared to inorganic salts of
FeIII [59]. It was demonstrated by mass-spectrometry that in 1:2 molar ratio solution of FeIII and
citric acid at pH 7 the dominant species is [Fe3OCit3H3]2- [60] or [Fe3Cit3H]2- [61]. The chemical

T
models for Fenton-like and photo-Fenton-like reactions mechanisms are still to be developed that

IP
take into account the real speciation of iron complexes in aqueous solutions providing the best
performance in degradation of water pollutants.

R
SC
Ultrasonic treatment during the Fenton reaction increases its efficiency in degradation of an azo
dye in 2.5 times [62]. The effect is attributed to additional hydroxyl radicals produced under the
action of ultrasound and to enhanced mass transport of reagents. According to results of many

U
studies, iron (III) oxalate can be the most active catalyst in photo-Fenton systems. Iron (III)
N
citrate also shows very good performance. FeIII in combinations with nitrilotriacetic acid (NTA),
A
EDTA and DETAPAC have questionable performance in comparison to standard photo-Fenton
system.
M
ED

Table 2. Most popular organic ligands used in Fenton- and photo-Fenton-like systems.

Structural formula Name of Activity in (photo-)Fenton

PT

protonated reagent and notes

ligand
E

Oxalic acid FeIII oxalate more active than

CC

citrate in photo-Fenton [63]

Malonic acid Smaller activity than for FeIII-
A

UV-H2O2 [64]
Succinic acid Less active than tartrate, more
active than FeIII-H2O2 [62]
Tartaric acid More active than FeIII
succinate, less active than
citrate [62]

17
 Citric acid (Cit) FeIIICit, m-cresol photolysis
365 nm, pH 6, 30 min [46];
more active than EDDS in
photo-Fenton [63]
NTA Less active than FeIII-H2O2 ,
more active than FeIIIEDTA
[62]
EDTA The enhancing effect of

T
EDTA needs to be checked

IP
EDDS 70 % conversion of BPA in 70
min compared to 350 min for

R
FeIII + H2O2 at pH 6.2 [65]

SC
DETAPAC,
DTPA

U
N
5-sulfosalicylic Upon attachment to polymers
acid with aminogroups forms
A
active heterogenized Fenton
M

catalyst.
Dipicolinic acid 30 min degradation of
ED

(DPA) quinoline with FeIII(DPA)2 +

H2O2 + UV, pH 5 [66]
TMC Not compared in aqueous
PT

systems.
E
CC

FeIII-EDDS-H2O2 system was suggested relatively recently for treatment of water at near neutral
pH. This suggestion is backed by biodegradability of EDDS complexes. However, more efficient
A

systems with degradation quantum yield similar to that of Fe III oxalate should be searched for
because its prominent absorption of visible solar light that can be used for water treatment. Even
a better choice could be a FeIII complex with polydentate inorganic ligands that are stable to RI
and can drive the reaction of pollutants degradation up to its completion.

18
7. Structural and electronic factors determining the high activity of dissolved
catalysts in Fenton and photo-Fenton reactions

Given the variety of ligands for iron (III) and iron (II) complexes in aqueous solutions, it is
important to develop deep understanding on the key properties of the complexes that determine
high efficiency in Fenton-like and photo-Fenton-like reactions. These properties can be related
with the number of coordination sites occupied and left unoccupied around the central atom,
types of ligands in the equatorial and axial positions relative to unoccupied coordinative sites,

T
extent and type of distortion of the coordination sphere.

IP
It is generally agreed upon that at least one or two coordination sites should be unoccupied or
occupied by a highly labile ligand in order for the Fenton-like reaction to proceed [67]. This

R
requirement corresponds to inner sphere mechanism of hydrogen peroxide reduction or oxoferryl

SC
species production. In several cases, the reaction of FeII complex with H2O2 proceeds efficiently
even for hexacoordinated complex without easily removed ligands that points out to the

U
possibility of outer sphere electron transfer in generation of RI [68].
N
Many iron complexes are suggested to have a significant part of their reactivity in Fenton
reaction due to the formation of high valence state ferryl LxFeIV=O. This species is more stable
A

than hydroxyl radical and can be decomposed unproductively via reactions with Fe II equation
M

(26) or with H2O2 equation (25). Therefore, it is imperative to increase the FeIV=O reactivity
towards organic compounds in equation (14) and decrease towards reactions (25) and (26).
ED

Several publications deal with the reactivity of ferryl complexes with hydrocarbons. It is found
that high spin state ferryl in quintet state is more reactive than in triplet state due to the lower
PT

energy of ferryl’s LUMO 3* [69]. The influence of the type of equatorial ligands and axial
ligand in trans position relative to Fe=O on reactivity towards hydrocarbons hydroxylation has
E

received large attention. Electron withdrawing ligands like water, BF3 or no ligand decrease the
CC

reaction barrier of C-H bond cleavage compared to electron-donating NH3 axial ligand in the
case the equatorial ligands are H2O [69]. [(H2O)5FeIV=O]2+ is a highly reactive species for
methane oxidation into methanol and is therefore a very potent oxidant for Fenton reaction [70].
A

Low field ligands containing oxygen atoms in equatorial position favor highly reactive high spin
state ferryl species, while -donating amine ligands favor triplet state [69]. However, in work
[71], such axial ligands as N3- and NCS- produced the lowest hydrogen abstraction barrier of
methane by FeIV=O in 5 and 3 pathways, respectively, for NH3 equatorial ligands. The lowest
G≠ = 19.9 kcal/mol for hydrogen atom abstraction was for the [(NH3)4(NCS)FeIV=O]+ complex

19
in the 5 pathway. The beneficial role of low field H2O ligands (E≠ = 5 kcal/mol) in comparison
to strong field NH3 ligands (E≠ = 28 kcal/mol) for H abstraction was confirmed in work [72].
However, relatively low free energy of activation of 11 to 20 kcal/mol was reported for strong
field equatorial NH3 ligands [73] and similar values for tetradentate N,N’-dimethyl-N,N’-bis(2-
pyridylmethyl)ethane (MEP) [67]. N4 cyclic nonheme ligand TMC allowed obtaining in
acetonitrile solution as high yields as 90 % of [(TMC)(CH3CN)FeIV=O] in the presence of 2,6-
lutidine as catalyst at -40°C [74]. This signifies a high stability of the RI with nitrogen ligands.

EDTA has received a large attention as a ligand for iron since it allows obtaining ferryl in high

T
yield in aqueous solutions of H2O2. Axial ligands of Feiv=O in EDTA complex are carboxyl

IP
groups oxygen atoms whereas the axial ligand is missing that makes the complex especially

R
reactive towards hydrogen atom abstraction from CH4 [75]. The fully protonated
[EDTAH4FeIV=O]2+ complex was calculated to have the lowest PES activation energy of 7 to 10

SC
kJ/mol for hydrogen atom abstraction from CH4 [75].

Dimeric [(EDTAH)FeII-FeII(EDTAH)]2- complex with hydrogen-bonded ligands is considered as

U
a precursor for dimeric high spin bis--ferryloxo complex [(EDTAH)FeIVO-OFeIV(EDTAH)]2-
N
that is a potent reagent for hydrogen atom abstraction from methane [76]. The calculated free
A
energy barrier for hydrogen abstraction is 28.2 kJ/mol that is smaller than for the corresponding
M

monomeric oxoferryl complex. Noting that very many researchers focused their research on
modeling the reactions of formation, structure and reaction of oxoferryl species (H2O)5FeIV=O2+,
(H2O)4(OH)FeIV=O+ using DFT, semiempirical and coupled cluster methods, one could conclude
ED

that the subject is well investigated and no new knowledge is obtained in recent publications
[13,29,51,52,56,70,72,77–85]. The PES energies and free energies obtained vary widely. The
PT

value of many available experimental and computational data could be, however, priced well if
one recalls that the true value is equal to mean data value and the deviation of mean value from a
E

true value decreases as the number of data points increases.

CC

Further research is needed to discover which ligands not only increase reactivity of ferryl in
reaction (14) but also decrease the rate of undesirable ferryl deactivation reactions (25) and (26).
A

Experimental and computational data suggests that nitrogen-coordinating equatorial ligands

allow facile obtaining ferryl complexes in high yield [86]. Therefore, ferryl deactivation
reactions are obviously retarded.

20
8. Structure of active sites of heterogeneous Fenton and photo-Fenton reaction
catalysts

Heterogeneous Fenton and photo-Fenton systems are very promising for water purification
because solid catalysts do not have the pH limitations typical for dissolved iron compounds, can
be readily separated from the treated water and reused. Table 3 lists a few examples of
heterogeneous Fenton and photo-Fenton catalysts. It should be noticed that highly dispersed
catalysts and photo-Fenton reaction allow obtaining very high conversion of water pollutants
into inorganic products. Presence of FeII is generally beneficial for obtaining fast and full

T
conversion of water pollutants. To facilitate the stage of FeIII to FeII reduction, hydroxylamine

IP
was added in some systems and this resulted in very fast conversion of water pollutants [31,87].

R
Creation of very small particles of iron containing materials is also considered important for high

SC
rate of water pollutants degradation.

Fe-ZSM-5 represents an astonishing example of heterogeneous Fenton catalyst and also a

U
thermal partial oxidation catalyst. It is demonstrated that the well known highly reactive -
oxygen in FeZSM-5 has the actual structure corresponding to oxoferryl moiety [88]. Iron atoms
N
in FeIVO-ZSM-5 have distorted octahedral coordination sphere of oxygen atoms. This high spin
A
quintet geometry resulted in a very small activation barrier of 7.0 kcal/mol for methane
M

hydroxylation via rebound mechanism. It can be pointed out that the structure of -ferryl oxygen
in FeZSM-5 corresponds to the best catalytic coordination sphere for iron in complexes as was
ED

discussed in section 7.

Interaction of iron component with alumina component was demonstrated to be beneficial for
PT

degradation of azo dyes in Fenton heterogeneous system containing Fe2O3/silica or

Fe2O3/Al2O3/silica catalysts despite of the reduced surface area [89]. This shows that alumina is
E

possibly a better support for Fenton catalysts than silica and Al-O-Fe structural motif may be a
CC

highly active catalytic site.

A

Table 3. Some of heterogeneous Fenton and photo-Fenton catalysts.

Material Material name Active sites or active References

principal components
component
-Fe2O3 Hematite (113) > (104) > (001), FeIII / [31,89–91]

21
 FeII
-FeOOH Limonite 300 Fe3O4, FeII >> FeIII [92,93]
-FeOOH Goethite FeII / FeIII [87]
/NH2OH
Fe3O4 Magnetite FeII, FeIII [7,94]
BiFeO3 DFO perovskite FeIII / FeII [94]
Fe2O3 Fe silicalite FeIII in nanocrystals [47]
FeZSM-5 FeZSM-5 FeIV=O [88]

T
Fe2O3 Fe2O3/HPS FeIII/FeII [31]

IP
Fe2O3/Al2O3/silica Fe2O3/Al2O3/silica FeIII/Al2O3 [95]
BiOCl BiOCl nanosheets Surface oxygen vacancies [96]

R
SC
An interesting surface Fenton reaction is reported for BiOCl nanosheets evacuated at 400 K for
60 min to create surface oxygen vacancies. Oxidation of benzoic and formic acid with surface

U
hydroxyl radicals produced with participation of H2O2 and BiII species was efficient in a wide pH
N
range and on both (001) and (010) exposed nanosheets [96]. A lot of additional work using
A
experimental and computational methods is required to design heterogeneous Fenton and photo-
Fenton catalysts that have high activity in complete mineralization of water pollutants and high
M

stability.
ED

9. Conclusions
PT

Consideration of modern literature on (photo-)Fenton(-like) systems involving Fe cations

demonstrated continuous interest to fundamental and applied aspects of these reactions. The
E

mechanism of organic compounds oxidation in these systems includes hydroxyl radicals OH˙
CC

and monomeric or dimerized oxoferryl FeIV=O species as reactive intermediates that can be
involved in different ratio depending on reagents concentration. The following fundamental
A

problems need research efforts.

1. Quantum chemical calculation of free energies and rate constants for all steps of Fenton and
photo-Fenton reactions. Checking on the possibilities of outer sphere electron transfer in OH˙
formation. Evaluation of the theoretical model by fitting to experimental kinetic curves.

22
2. Enrichment of the mechanisms of Fenton(-like) and photo-Fenton(-like) reactions with steps
that are required for transforming the reagents into the products without missing important
intermediate stages.

3. Determine the causes for the changes in the mechanism of Fenton reaction with reagents
concentrations and pH.

The following applied research is needed for advancing (photo-)Fenton(-like) systems into
industrial use.

T
1. Investigation of the effects of special hydrodynamics conditions for obtaining high rates of

IP
pollutants degradation in Fenton and Fenton-like systems.

R
2. Design of inorganic ligands for photo-Fenton-like homogeneous systems.

SC
3. Design of heterogeneous catalysts with high number and high activity of active sites for
photo-Fenton pollutants degradation.

U
N
A
M
ED
E PT
CC
A

23
References

[1] J.L. Wang, L.J. Xu, Advanced Oxidation Processes for Wastewater Treatment: Formation of
Hydroxyl Radical and Application, Crit. Rev. Environ. Sci. Technol. 42 (2012) 251–325.
doi:10.1080/10643389.2010.507698.
[2] S. Goldstein, D. Meyerstein, G. Czapski, The Fenton reagents, Free Radic. Biol. Med. 15
(1993) 435–445. doi:10.1016/0891-5849(93)90043-T.
[3] A. Babuponnusami, K. Muthukumar, A review on Fenton and improvements to the Fenton
process for wastewater treatment, J. Environ. Chem. Eng. 2 (2014) 557–572.
doi:10.1016/j.jece.2013.10.011.
[4] J.J. Pignatello, E. Oliveros, A. MacKay, Advanced Oxidation Processes for Organic
Contaminant Destruction Based on the Fenton Reaction and Related Chemistry, Crit. Rev.

T
Environ. Sci. Technol. 36 (2006) 1–84. doi:10.1080/10643380500326564.

IP
[5] L. Clarizia, D. Russo, I. Di Somma, R. Marotta, R. Andreozzi, Homogeneous photo-Fenton
processes at near neutral pH: A review, Appl. Catal. B Environ. 209 (2017) 358–371.
doi:10.1016/j.apcatb.2017.03.011.

R
[6] N. Wang, T. Zheng, G. Zhang, P. Wang, A review on Fenton-like processes for organic
wastewater treatment, J. Environ. Chem. Eng. 4 (2016) 762–787.

SC
doi:10.1016/j.jece.2015.12.016.
[7] J. He, X. Yang, B. Men, D. Wang, Interfacial mechanisms of heterogeneous Fenton reactions
catalyzed by iron-based materials: A review, J. Environ. Sci. 39 (2016) 97–109.
doi:10.1016/j.jes.2015.12.003.
U
[8] S. Giannakis, M.I. Polo López, D. Spuhler, J.A. Sánchez Pérez, P. Fernández Ibáñez, C.
N
Pulgarin, Solar disinfection is an augmentable, in situ -generated photo-Fenton reaction—
Part 1: A review of the mechanisms and the fundamental aspects of the process, Appl. Catal.
A
B Environ. 199 (2016) 199–223. doi:10.1016/j.apcatb.2016.06.009.
[9] A.D. Bokare, W. Choi, Review of iron-free Fenton-like systems for activating H2O2 in
M

advanced oxidation processes, J. Hazard. Mater. 275 (2014) 121–135.

doi:10.1016/j.jhazmat.2014.04.054.
[10] F. Haber, J. Weiss, Uber die Katalyse des Hydroperoxydes, Naturwissenschaften. 20
ED

(1932) 948–950. doi:10.1007/BF01504715.

[11] W.C. Bray, M.H. Gorin, FERRYL ION, A COMPOUND OF TETRAVALENT IRON, J.
Am. Chem. Soc. 54 (1932) 2124–2125. doi:10.1021/ja01344a505.
[12] S. Enami, Y. Sakamoto, A.J. Colussi, Fenton chemistry at aqueous interfaces, Proc. Natl.
PT

Acad. Sci. 111 (2014) 623–628.

[13] F. Buda, B. Ensing, M. Gribnau, E.J. Baerends, DFT study of the active intermediate in
the Fenton reaction, Chem.- Eur. J. 7 (2001) 2775–2783.
E

[14] P. Wardman, L.P. Candeias, Fenton Chemistry: An Introduction, Radiat. Res. 145 (1996)
523. doi:10.2307/3579270.
CC

[15] W.H. Koppenol, The Haber-Weiss cycle – 70 years later, Redox Rep. 6 (2001) 229–234.
doi:10.1179/135100001101536373.
[16] C. Walling, G.M. El-Taliawi, R.A. Johnson, Fenton’s reagent. IV. Structure and
reactivity relations in the reactions of hydroxyl radicals and the redox reactions of radicals, J.
A

Am. Chem. Soc. 96 (1974) 133–139. doi:10.1021/ja00808a022.

[17] C. Walling, Fenton’s reagent revisited, Acc. Chem. Res. 8 (1975) 125–131.
doi:10.1021/ar50088a003.
[18] A. Machulek Jr, F.H. Quina, F. Gozzi, V.O. Silva, L.C. Friedrich, J.E. Moraes,
Fundamental mechanistic studies of the photo-Fenton reaction for the degradation of organic
pollutants, in: Org. Pollut. Ten Years Stockh. Conv.-Environ. Anal. Update, InTech, 2012.
https://www.intechopen.com/download/pdf/29377 (accessed August 31, 2017).

24
[19] W.C. Bray, The Interaction of Ozone and Hydrogen Peroxide in Aqueous Solution, J.
Am. Chem. Soc. 60 (1938) 82–87. doi:10.1021/ja01268a027.
[20] C. Mansano-Weiss, H. Cohen, D. Meyerstein, Reactions of peroxyl radicals with
Fe(H2O)62+, J. Inorg. Biochem. 91 (2002) 199–204. doi:10.1016/S0162-0134(02)00460-9.
[21] M.L. Kremer, Mechanism of the Fenton reaction. Evidence for a new intermediate, Phys.
Chem. Chem. Phys. 1 (1999) 3595–3605. doi:10.1039/a903915e.
[22] B. Halliwell, J.M.C. Gutteridge, Biologically relevant metal ion-dependent hydroxyl
radical generation An update, FEBS Lett. 307 (1992) 108–112. doi:10.1016/0014-
5793(92)80911-Y.
[23] A. Cabrera Reina, L. Santos-Juanes Jordá, J.L. García Sánchez, J.L. Casas López, J.A.
Sánchez Pérez, Modelling photo-Fenton process for organic matter mineralization, hydrogen
peroxide consumption and dissolved oxygen evolution, Appl. Catal. B Environ. 119–120

T
(2012) 132–138. doi:10.1016/j.apcatb.2012.02.021.
[24] S.H. Bossmann, E. Oliveros, S. Göb, S. Siegwart, E.P. Dahlen, L. Payawan, M. Straub,

IP
M. Wörner, A.M. Braun, New Evidence against Hydroxyl Radicals as Reactive
Intermediates in the Thermal and Photochemically Enhanced Fenton Reactions, J. Phys.

R
Chem. A. 102 (1998) 5542–5550. doi:10.1021/jp980129j.
[25] H. Lee, H.-J. Lee, D.L. Sedlak, C. Lee, pH-Dependent reactivity of oxidants formed by

SC
iron and copper-catalyzed decomposition of hydrogen peroxide, Chemosphere. 92 (2013)
652–658. doi:10.1016/j.chemosphere.2013.01.073.
[26] E. Siedlecka, A. Wieckowska, P. Stepnowski, Influence of inorganic ions on MTBE
degradation by Fenton’s reagent, J. Hazard. Mater. 147 (2007) 497–502.
doi:10.1016/j.jhazmat.2007.01.044.
U
[27] J. Kiwi, A. Lopez, V. Nadtochenko, Mechanism and Kinetics of the OH-Radical
N
Intervention during Fenton Oxidation in the Presence of a Significant Amount of Radical
Scavenger (Cl - ), Environ. Sci. Technol. 34 (2000) 2162–2168. doi:10.1021/es991406i.
A
[28] T.J. Conocchioli, E.J. Hamilton, N. Sutin, The Formation of Iron(IV) in the Oxidation of
Iron(II) 1, J. Am. Chem. Soc. 87 (1965) 926–927. doi:10.1021/ja01082a050.
M

[29] A.S. Petit, R.C.R. Pennifold, J.N. Harvey, Electronic Structure and Formation of Simple
Ferryloxo Complexes: Mechanism of the Fenton Reaction, Inorg. Chem. 53 (2014) 6473–
6481. doi:10.1021/ic500379r.
ED

[30] L. Bernasconi, A. Kazaryan, P. Belanzoni, E.J. Baerends, Catalytic Oxidation of Water

with High-Spin Iron(IV)–Oxo Species: Role of the Water Solvent, ACS Catal. 7 (2017)
4018–4025. doi:10.1021/acscatal.7b00568.
PT

[31] Z. Miao, S. Tao, Y. Wang, Y. Yu, C. Meng, Y. An, Hierarchically porous silica as an
efficient catalyst carrier for high performance vis-light assisted Fenton degradation,
Microporous Mesoporous Mater. 176 (2013) 178–185.
doi:10.1016/j.micromeso.2013.04.009.
E

[32] G.V. Buxton, C.L. Greenstock, W.P. Helman, A.B. Ross, Critical Review of rate
CC

constants for reactions of hydrated electrons, hydrogen atoms and hydroxyl radicals (⋅OH/⋅O
−
in Aqueous Solution, J. Phys. Chem. Ref. Data. 17 (1988) 513–886. doi:10.1063/1.555805.
[33] I.P. Ivanova, S.V. Trofimova, I.M. Piskarev, N.A. Aristova, O.E. Burhina, O.O.
Soshnikova, Mechanism of chemiluminescence in Fenton reaction, J. Biophys. Chem. 03
A

(2012) 88–100. doi:10.4236/jbpc.2012.31011.

[34] M.R. Rojas, F. Pérez, D. Whitley, R.G. Arnold, A.E. Sáez, Modeling of advanced
oxidation of trace organic contaminants by hydrogen peroxide photolysis and Fenton’s
reaction, Ind. Eng. Chem. Res. 49 (2010) 11331–11343.
[35] Z.B. Alfassi, ed., Peroxyl radicals, Wiley, Chichester ; New York, 1997.
[36] S. Rachmilovich-Calis, A. Masarwa, N. Meyerstein, D. Meyerstein, The Fenton Reaction
in Aerated Aqueous Solutions Revisited, Eur. J. Inorg. Chem. 2005 (2005) 2875–2880.
doi:10.1002/ejic.200500097.

25
[37] M.C.F. Wander, J.D. Kubicki, A.E. Clark, M.A.A. Schoonen, Ferrous Iron Reduction of
Superoxide, A Proton-Coupled Electron-Transfer Four-Point Test, J. Phys. Chem. A. 113
(2009) 1020–1025. doi:10.1021/jp806842f.
[38] T. Loegager, J. Holcman, K. Sehested, T. Pedersen, Oxidation of ferrous ions by ozone in
acidic solutions, Inorg. Chem. 31 (1992) 3523–3529. doi:10.1021/ic00043a009.
[39] H. Dunford, Oxidations of iron(II)/(III) by hydrogen peroxide: from aquo to enzyme,
Coord. Chem. Rev. 233–234 (2002) 311–318. doi:10.1016/S0010-8545(02)00024-3.
[40] F. Mazille, Development of a Photo-Fenton Catalyst Supported on Modified Polymer
Films, (2010). http://infoscience.epfl.ch/record/147971 (accessed August 31, 2017).
[41] I. Yamazaki, L.H. Piette, ESR spin-trapping studies on the reaction of Fe2+ ions with
H2O2-reactive species in oxygen toxicity in biology, J. Biol. Chem. 265 (1990) 13589–
13594.

T
[42] M.J. Burkitt, ESR spin trapping studies into the nature of the oxidizing species formed in
the Fenton reaction: pitfalls associated with the use of 5,5-dimethyl-1-pyrroline-N-oxide in

IP
the detection of the hydroxyl radical, Free Radic. Res. Commun. 18 (1993) 43–57.
[43] X.-L. Sun, X.-R. Huang, J.-L. Li, R.-P. Huo, C.-C. Sun, Mechanism Insights of Ethane
C–H Bond Activations by Bare [Fe III ═O] + : Explicit Electronic Structure Analysis, J. Phys.

R
Chem. A. 116 (2012) 1475–1485. doi:10.1021/jp2120302.

SC
[44] P. Salgado, V. Melin, Y. Durán, H. Mansilla, D. Contreras, The Reactivity and Reaction
Pathway of Fenton Reactions Driven by Substituted 1,2-Dihydroxybenzenes, Environ. Sci.
Technol. 51 (2017) 3687–3693. doi:10.1021/acs.est.6b05388.
[45] W. Song, M. Cheng, J. Ma, W. Ma, C. Chen, J. Zhao, Decomposition of Hydrogen
U
Peroxide Driven by Photochemical Cycling of Iron Species in Clay, Environ. Sci. Technol.
40 (2006) 4782–4787. doi:10.1021/es060624q.
N
[46] N. Seraghni, S. Belattar, Y. Mameri, N. Debbache, T. Sehili, Fe(III)-Citrate-Complex-
Induced Photooxidation of 3-Methylphenol in Aqueous Solution, Int. J. Photoenergy. 2012
A
(2012) 1–10. doi:10.1155/2012/630425.
[47] K.A. Sashkina, A.V. Polukhin, V.S. Labko, A.B. Ayupov, A.I. Lysikov, E.V.
M

Parkhomchuk, Fe-silicalites as heterogeneous Fenton-type catalysts for radiocobalt removal

from EDTA chelates, Appl. Catal. B Environ. 185 (2016) 353–361.
doi:10.1016/j.apcatb.2015.12.038.
ED

[48] S. Rtimi, C. Pulgarin, R. Sanjines, J. Kiwi, Novel FeOx–polyethylene transparent films:

synthesis and mechanism of surface regeneration, RSC Adv. 5 (2015) 80203–80211.
doi:10.1039/C5RA14503A.
PT

[49] M. Sun, C. Chu, F. Geng, X. Lu, J. Qu, J. Crittenden, M. Elimelech, J.-H. Kim,
Reinventing Fenton Chemistry: Iron Oxychloride Nanosheet for pH-Insensitive H 2 O 2
Activation, Environ. Sci. Technol. Lett. (2018). doi:10.1021/acs.estlett.8b00065.
[50] U. El-Ayaan, R. F. Jameson, W. Linert, A kinetic study of the reaction between
E

noradrenaline and iron(III): an example of parallel inner- and outer-sphere electron transfer,
CC

J. Chem. Soc. Dalton Trans. (1998) 1315. doi:10.1039/a708639c.

[51] B. Ensing, F. Buda, P.E. Blöchl, E.J. Baerends, A Car–Parrinello study of the formation
of oxidizing intermediates from Fenton’s reagent in aqueous solution, Phys. Chem. Chem.
Phys. 4 (2002) 3619–3627. doi:10.1039/b201864k.
A

[52] B. Ensing, F. Buda, P. Blöchl, E.J. Baerends, Chemical Involvement of Solvent Water
Molecules in Elementary Steps of the Fenton Oxidation Reaction, Angew. Chem. Int. Ed. 40
(2001) 2893–2895. doi:10.1002/1521-3773(20010803)40:15<2893::AID-
ANIE2893>3.0.CO;2-B.
[53] M.L. Kremer, Promotion of the fenton reaction by Cu2+ ions: Evidence for
intermediates, Int. J. Chem. Kinet. 38 (2006) 725–736. doi:10.1002/kin.20205.
[54] P. Comba, G. Rajaraman, H. Rohwer, A Density Functional Theory Study of the
Reaction of the Biomimetic Iron(II) Complex of a Tetradentate Bispidine Ligand with H 2 O
2, Inorg. Chem. 46 (2007) 3826–3838. doi:10.1021/ic061129y.

26
[55] H. Tang, J. Guan, H. Liu, X. Huang, Analysis of an alternative to the H-atom abstraction
mechanism in methane C–H bond activation by nonheme iron(iv)-oxo oxidants, Dalton
Trans. 42 (2013) 10260. doi:10.1039/c3dt50866h.
[56] H. Tang, J. Guan, H. Liu, X. Huang, Comparative Insight into Electronic Properties and
Reactivities toward C–H Bond Activation by Iron(IV)–Nitrido, Iron(IV)–Oxo, and Iron(IV)–
Sulfido Complexes: A Theoretical Investigation, Inorg. Chem. 52 (2013) 2684–2696.
doi:10.1021/ic302766f.
[57] H. Chen, K.-B. Cho, W. Lai, W. Nam, S. Shaik, Dioxygen Activation by a Non-Heme
Iron(II) Complex: Theoretical Study toward Understanding Ferric–Superoxo Complexes, J.
Chem. Theory Comput. 8 (2012) 915–926. doi:10.1021/ct300015y.
[58] S. Croft, B.C. Gilbert, J.R.L. Smith, J.K. Stell, W.R. Sanderson, Mechanisms of peroxide
stabilization. An investigation of some reactions of hydrogen peroxide in the presence of

T
aminophosphonic acids, J. Chem. Soc. Perkin Trans. 2. (1992) 153.
doi:10.1039/p29920000153.

IP
[59] I. Gautier-luneau, P. Bertet, A. Jeunet, G. Serratrice, J.-L. Pierre, Iron-citrate complexes
and free radicals generation: Is citric acid an innocent additive in foods and drinks?,

R
BioMetals. 20 (2007) 793–796. doi:10.1007/s10534-006-9042-y.
[60] A.M.N. Silva, X. Kong, M.C. Parkin, R. Cammack, R.C. Hider, Iron(iii) citrate

SC
speciation in aqueous solution, Dalton Trans. (2009) 8616. doi:10.1039/b910970f.
[61] I. Gautier-Luneau, C. Merle, D. Phanon, C. Lebrun, F. Biaso, G. Serratrice, J.-L. Pierre,
New Trends in the Chemistry of Iron(III) Citrate Complexes: Correlations between X-ray
Structures and Solution Species Probed by Electrospray Mass Spectrometry and Kinetics of
U
Iron Uptake from Citrate by Iron Chelators, Chem. - Eur. J. 11 (2005) 2207–2219.
doi:10.1002/chem.200401087.
N
[62] T. Zhou, T.-T. Lim, X. Wu, Sonophotolytic degradation of azo dye reactive black 5 in an
ultrasound/UV/ferric system and the roles of different organic ligands, Water Res. 45 (2011)
A
2915–2924. doi:10.1016/j.watres.2011.03.008.
[63] P.A. Soares, M. Batalha, S.M.A.G.U. Souza, R.A.R. Boaventura, V.J.P. Vilar,
M

Enhancement of a solar photo-Fenton reaction with ferric-organic ligands for the treatment
of acrylic-textile dyeing wastewater, J. Environ. Manage. 152 (2015) 120–131.
doi:10.1016/j.jenvman.2015.01.032.
ED

[64] D. Xiao, Y. Guo, X. Lou, C. Fang, Z. Wang, J. Liu, Distinct effects of oxalate versus
malonate on the iron redox chemistry: Implications for the photo-Fenton reaction,
Chemosphere. 103 (2014) 354–358. doi:10.1016/j.chemosphere.2013.11.069.
PT

[65] W. Huang, M. Brigante, F. Wu, C. Mousty, K. Hanna, G. Mailhot, Assessment of the

Fe(III)–EDDS Complex in Fenton-Like Processes: From the Radical Formation to the
Degradation of Bisphenol A, Environ. Sci. Technol. 47 (2013) 1952–1959.
doi:10.1021/es304502y.
E

[66] P.H. Ramos, F.A. La Porta, E.C. de Resende, J.O.S. Giacoppo, M.C. Guerreiro, T.C.
CC

Ramalho, Fe-DPA as Catalyst for Oxidation of Organic Contaminants: Evidence of

Homogeneous Fenton Process: Fe-DPA as Catalyst for Oxidation of Organic Contaminants,
Z. Für Anorg. Allg. Chem. 641 (2015) 780–785. doi:10.1002/zaac.201400578.
[67] J. Wang, Y. Zhao, P.-H. Lee, Computational analysis of site differences in selective
A

aliphatic C–H hydroxylation by nonheme iron–oxo complexes, Phys Chem Chem Phys. 19
(2017) 13924–13930. doi:10.1039/C7CP01479A.
[68] C.-W. Tse, T.W.-S. Chow, Z. Guo, H.K. Lee, J.-S. Huang, C.-M. Che, Nonheme Iron
Mediated Oxidation of Light Alkanes with Oxone: Characterization of Reactive Oxoiron(IV)
Ligand Cation Radical Intermediates by Spectroscopic Studies and DFT Calculations,
Angew. Chem. Int. Ed. 53 (2014) 798–803. doi:10.1002/anie.201305153.
[69] L. Bernasconi, M.J. Louwerse, E.J. Baerends, The Role of Equatorial and Axial Ligands
in Promoting the Activity of Non-Heme Oxidoiron(IV) Catalysts in Alkane Hydroxylation,
Eur. J. Inorg. Chem. 2007 (2007) 3023–3033. doi:10.1002/ejic.200601238.
27
[70] B. Ensing, F. Buda, M.C.M. Gribnau, E.J. Baerends, Methane-to-Methanol Oxidation by
the Hydrated Iron(IV) Oxo Species in Aqueous Solution: A Combined DFT and
Car−Parrinello Molecular Dynamics Study, J. Am. Chem. Soc. 126 (2004) 4355–4365.
doi:10.1021/ja038865a.
[71] H. Tang, J. Guan, L. Zhang, H. Liu, X. Huang, The effect of the axial ligand on distinct
reaction tunneling for methane hydroxylation by nonheme iron(iv)–oxo complexes, Phys.
Chem. Chem. Phys. 14 (2012) 12863. doi:10.1039/c2cp42423a.
[72] A. Kazaryan, E.J. Baerends, Ligand Field Effects and the High Spin–High Reactivity
Correlation in the H Abstraction by Non-Heme Iron(IV)–Oxo Complexes: A DFT Frontier
Orbital Perspective, ACS Catal. 5 (2015) 1475–1488. doi:10.1021/cs501721y.
[73] C. Geng, S. Ye, F. Neese, Analysis of Reaction Channels for Alkane Hydroxylation by
Nonheme Iron(IV)-Oxo Complexes, Angew. Chem. Int. Ed. 49 (2010) 5717–5720.

T
doi:10.1002/anie.201001850.
[74] F. Li, J. England, L. Que, Near-Stoichiometric Conversion of H 2 O 2 to Fe IV =O at a

IP
Nonheme Iron(II) Center. Insights into the O−O Bond Cleavage Step, J. Am. Chem. Soc.
132 (2010) 2134–2135. doi:10.1021/ja9101908.

R
[75] L. Bernasconi, E.J. Baerends, The EDTA Complex of Oxidoiron(IV) as Realisation of an
Optimal Ligand Environment for High Activity of FeO2+, Eur. J. Inorg. Chem. 2008 (2008)

SC
1672–1681. doi:10.1002/ejic.200701135.
[76] L. Bernasconi, P. Belanzoni, E.J. Baerends, An abiotic analogue of the diiron(iv)oxo
“diamond core” of soluble methane monooxygenase generated by direct activation of O2 in
aqueous Fe(ii)/EDTA solutions: thermodynamics and electronic structure, Phys. Chem.
U
Chem. Phys. 13 (2011) 15272. doi:10.1039/c1cp21244c.
[77] H. Kornweitz, A. Burg, D. Meyerstein, Plausible Mechanisms of the Fenton-Like
N
Reactions, M = Fe(II) and Co(II), in the Presence of RCO 2 – Substrates: Are OH • Radicals
Formed in the Process?, J. Phys. Chem. A. 119 (2015) 4200–4206. doi:10.1021/jp512826f.
A
[78] P. Mignon, M. Pera-Titus, H. Chermette, Oxo iron(iv) as an oxidative active intermediate
of p-chlorophenol in the Fenton reaction: a DFT study, Phys. Chem. Chem. Phys. 14 (2012)
M

3766. doi:10.1039/c2cp23231f.
[79] F. Buda, B. Ensing, M.C.M. Gribnau, E.J. Baerends, O2 Evolution in the Fenton
Reaction, Chem. - Eur. J. 9 (2003) 3436–3444. doi:10.1002/chem.200204444.
ED

[80] X. Sun, C. Geng, R. Huo, U. Ryde, Y. Bu, J. Li, Large Equatorial Ligand Effects on C–H
Bond Activation by Nonheme Iron(IV)-oxo Complexes, J. Phys. Chem. B. 118 (2014) 1493–
1500. doi:10.1021/jp410727r.
PT

[81] V. Kovalskii, A. Shubin, Y. Chen, D. Ovchinnikov, S.P. Ruzankin, J. Hasegawa, I.

Zilberberg, V.N. Parmon, Hidden radical reactivity of the [FeO] 2+ group in the H-
abstraction from methane: DFT and CASPT2 supported mechanism by the example of
model iron (hydro)oxide species, Chem. Phys. Lett. 679 (2017) 193–199.
E

doi:10.1016/j.cplett.2017.05.002.
CC

[82] L. Bernasconi, E.J. Baerends, Generation of Ferryl Species through Dioxygen Activation
in Iron/EDTA Systems: A Computational Study, Inorg. Chem. 48 (2009) 527–540.
doi:10.1021/ic800998n.
[83] B. Ensing, F. Buda, E.J. Baerends, Fenton-like Chemistry in Water: Oxidation Catalysis
A

by Fe(III) and H 2 O 2, J. Phys. Chem. A. 107 (2003) 5722–5731. doi:10.1021/jp0267149.

[84] H. Bataineh, O. Pestovsky, A. Bakac, Electron Transfer Reactivity of the Aqueous
Iron(IV)–Oxo Complex. Outer-Sphere vs Proton-Coupled Electron Transfer, Inorg. Chem.
55 (2016) 6719–6724. doi:10.1021/acs.inorgchem.6b00966.
[85] B. Ensing, E.J. Baerends, Reaction Path Sampling of the Reaction between Iron(II) and
Hydrogen Peroxide in Aqueous Solution, J. Phys. Chem. A. 106 (2002) 7902–7910.
doi:10.1021/jp025833l.
[86] H. Hirao, F. Li, L. Que, K. Morokuma, Theoretical Study of the Mechanism of
Oxoiron(IV) Formation from H 2 O 2 and a Nonheme Iron(II) Complex: O–O Cleavage
28
 Involving Proton-Coupled Electron Transfer, Inorg. Chem. 50 (2011) 6637–6648.
doi:10.1021/ic200522r.
[87] X. Hou, X. Huang, F. Jia, Z. Ai, J. Zhao, L. Zhang, Hydroxylamine Promoted Goethite
Surface Fenton Degradation of Organic Pollutants, Environ. Sci. Technol. 51 (2017) 5118–
5126. doi:10.1021/acs.est.6b05906.
[88] A. Rosa, G. Ricciardi, E.J. Baerends, Is [FeO] 2+ the Active Center Also in Iron
Containing Zeolites? A Density Functional Theory Study of Methane Hydroxylation
Catalysis by Fe-ZSM-5 Zeolite, Inorg. Chem. 49 (2010) 3866–3880. doi:10.1021/ic1000073.
[89] T.V. Kon’kova, M.G. Gordienko, M.B. Alekhina, N.V. Men’shutina, Catalytic properties
of Fe/SiO2–Al2O3 systems, obtained via sol–gel method, Russ. J. Phys. Chem. A. 91 (2017)
468–471. doi:10.1134/S0036024417030141.
[90] J.Y.T. Chan, S.Y. Ang, E.Y. Ye, M. Sullivan, J. Zhang, M. Lin, Heterogeneous photo-

T
Fenton reaction on hematite (α-Fe 2 O 3 ){104}, {113} and {001} surface facets, Phys Chem
Chem Phys. 17 (2015) 25333–25341. doi:10.1039/C5CP03332B.

IP
[91] M.S. Vasilyeva, V.S. Rudnev, A.A. Zvereva, K.N. Kilin, A.A. Sergeev, K.A. Sergeeva,
A.V. Nepomnyaschiy, S.S. Voznesenskiy, A.Y. Ustinov, Characterization and photocatalytic

R
activity of SiO2, FeOx coatings formed by plasma electrolytic oxidation of titanium, Surf.
Coat. Technol. 307 (2016) 1310–1314. doi:10.1016/j.surfcoat.2016.06.022.

SC
[92] W. Ferraz, L.C.A. Oliveira, R. Dallago, L. da Conceição, Effect of organic acid to
enhance the oxidative power of the fenton-like system: Computational and empirical
evidences, Catal. Commun. 8 (2007) 131–134. doi:10.1016/j.catcom.2006.05.038.
[93] W.F. de Souza, I.R. Guimarães, L.C.A. Oliveira, M.C. Guerreiro, A.L.N. Guarieiro,
U
K.T.G. Carvalho, Natural and H2-reduced limonite for organic oxidation by a Fenton-like
system: Mechanism study via ESI-MS and theoretical calculations, J. Mol. Catal. Chem. 278
N
(2007) 145–151. doi:10.1016/j.molcata.2007.09.003.
[94] W. Luo, L. Zhu, N. Wang, H. Tang, M. Cao, Y. She, Efficient Removal of Organic
A
Pollutants with Magnetic Nanoscaled BiFeO 3 as a Reusable Heterogeneous Fenton-Like
Catalyst, Environ. Sci. Technol. 44 (2010) 1786–1791. doi:10.1021/es903390g.
M

[95] T.V. Kon’kova, M.G. Gordienko, M.B. Alekhina, N.V. Men’shutina, S.D. Kirik,
Mesoporous silica based catalysts for the oxidation of azodyes in waste water, Catal. Ind. 8
(2016) 128–133. doi:10.1134/S2070050416020069.
ED

[96] H. Li, J. Shang, Z. Yang, W. Shen, Z. Ai, L. Zhang, Oxygen Vacancy Associated Surface
Fenton Chemistry: Surface Structure Dependent Hydroxyl Radicals Generation and
Substrate Dependent Reactivity, Environ. Sci. Technol. 51 (2017) 5685–5694.
PT

doi:10.1021/acs.est.7b00040.
E
CC
A

29