Applied Surface Science 401 (2017) 283–296

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Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

Full Length Article

Surface treatments of metal supports for photocatalysis applications

Francesco Montecchio a,∗ , Don Chinungi a , Roberto Lanza b , Klas Engvall a
a
KTH, Royal Institute of Technology, Dept. of Chemical Engineering and Technology, 100 44 Stockholm, Sweden
b
Verdant Chemical Technologies AB, 114 28 Stockholm, Sweden

a r t i c l e i n f o a b s t r a c t

Article history: One of the most important challenges, for scaling up a photocatalytic system for VOCs abatement to
Received 19 September 2016 full-scale, is the design of a suitable photocatalyst support. The support has to firmly immobilize the
Received in revised form photocatalyst, without using an organic adhesive, and should also withstand relatively high mechanical
24 December 2016
stresses. Metals may be effectively implemented as a support material, after a corrugation of the surface
Accepted 30 December 2016
with electrochemical treatments. In the present work, we treated stainless steel and aluminum sup-
Available online 4 January 2017
ports, evaluating the surface modifications due to the electrochemical treatments, with scanning electron
microscopy (SEM) and confocal microscopy. Five samples showing the highest degree of restructuring
Keywords:
Photocatalysis
were selected and spray coated with P25, a TiO2 photocatalyst, evaluating the mechanical stability of the
VOCs abatement coating with a standard tape test method. One particular stainless steel sample presented a superior sur-
Photocatalytic support face restructuring and coating stability. The photocatalytic activity of this sample, evaluated measuring
Electrochemical treatments the complete oxidation of acetaldehyde, was tested for 15 h, and compared with sample of TiO2 -P25 on a
Surface restructuring ceramic support. The stainless steel exhibited a constant performance after an initial stabilization period.
Coating stability The stainless steel sample showed a slightly higher activity, due to the surface restructuring, increasing
the irradiated area available for the coated photocatalyst.
© 2017 Elsevier B.V. All rights reserved.

1. Introduction The emitted VOCs, is also involved in reactions, producing ozone

Urban air pollution, constituting an important hazard for human
health, is one of the most challenging environmental issues the
last few decades. The WHO (World Health Organization) states
that several hundred thousand deaths per year are attributed to
air pollution, a number higher than any other environmental issue
for developed countries [1–4]. Furthermore, making the issue even
more challenging, urban air pollution generally involves a broad
range of compounds from numerous sources, making it hard to
pinpoint the exact cause of environmental hazardous pollutants
[5].
Among other compounds, VOCs (Volatile Organic Compounds)
constitute a very important category of air pollutant. They are
present in local areas of the atmosphere and may be very toxic
and hazardous even at very low concentrations.
The complexity of an emitted VOC mixture and the toxicity of
single compounds may create synergies enhancing the hazard of
the whole mixture, sometimes resulting in toxic levels higher than
those of well-known toxic compounds, such as benzene [6].
∗ Corresponding author.
E-mail address: fmon@kth.se (F. Montecchio).
and smog at ground level, caused by the reaction of NO, VOCs
and sulfur compounds [7–9]. Since ozone is a strong oxidant, it
directly attacks proteins and lipids or activates intracellular oxi-
dation mechanisms [10]. Furthermore, smog and particulates are
harmful for the respiratory and cardiovascular systems [10].
Another environmental issue, related to VOCs, is odor emission.
Some chemical compounds have a very low odor threshold [11–13],
often in the ppb range, making the VOCs emissions very odorous. In
recent years, the awareness of this issue has increased, manifested
as a growing number of complaints and stricter environmental local
legislations [14].
There are many different sources of VOCs emission, which
may be grouped in four different categories: power generation,
transportation, residential and industrial processes [15]. For all
these categories, constantly increasing VOCs emissions have been
recorded in the last year, with the industrial sector dominating
[15,16]. It is therefore crucial to efficiently treat the industrial emis-
sions, possibly with green technologies [17]. Catalytic and thermal
incineration has been widely used in the past to purify the industrial
exhausts [18]. However, these technologies are neither efficient,
due to a significant heat up of the whole gas to high temperature,
nor environmental friendly, due to a general use of fossil fuel for
supplying the heat. Photocatalysis, based on TiO2 photocatalysts,

http://dx.doi.org/10.1016/j.apsusc.2016.12.233
0169-4332/© 2017 Elsevier B.V. All rights reserved.
284 F. Montecchio et al. / Applied Surface Science 401 (2017) 283–296
offers a promising alternative for VOCs abatement [19]. The light
irradiation on the photocatalytic surface induces a very fast oxi-
dation reaction already at room temperature, due to formation of
hydroxyl radicals [20]. Therefore, there is no need for heating up
the gas stream, thus avoiding the use of fossil fuel and, at the same
time, reducing the CO2 emissions. The final result is a significantly
more environmentally friendly mitigation process.
When photocatalysis is used under UV light, it is possible to com-
bine this technology with ozonation, using the UV lamps both for
ozone generation and for activation of the photocatalyst [21–23].
This combination significantly increases the efficiency of the VOCs
removal, making it suitable for an industrial application. There are,
however, a few challenges to be addressed before utilizing the tech-
nology in operational full-scale photocatalytic systems. One of the
most important challenges is the design of an appropriate pho-
tocatalyst support. To be suitable for full-scale applications, the
support needs to fulfill several requirements. First, it needs to firmly
immobilize the photocatalyst, without using adhesives that may be
degraded by the UV light, which is the case for organic adhesives
[24]. The photocatalyst also needs to be efficiently exposed to the
light, maximizing the irradiated surface area, and thus also max-
imizing the activity of the catalyst. Furthermore, a close contact
between the VOCs and the catalyst needs to be ensured, minimiz-
ing the mass transfer limitations between the bulk gas phase and
the surface. In a full-scale UV reactor, the airflow could reach rel-
atively high speed, up to 10 m/s. It is therefore important that the
support withstands the mechanical stresses generated, which may
break fragile supports. Finally, the cost of the whole system needs
to be minimized. Both the manufacturing process of the reactor
and the materials for the support need to be evaluated in order to
develop a cost-effective solution.
Different materials can be used as photocatalyst support [25].
Previously, glass and quartz have been used in different forms:
beads, fibers, pellets or sheets. Ceramic materials have also been
widely investigated, especially cyclosilicates as cordierite, or phyl-
losilicates as organoclays. Metals are another important category
investigated, especially stainless steel. The porosity of ceramic and
glass supports, generally, simplifies the coating procedure, mak-
ing it attractive for use in R&D at lab scale. Traditional dip-coating
or pipetting procedures may then be applied to achieve a coating
stable enough for laboratory experiments [26,27]. In the case of
metallic surfaces, the general lack of porosity makes it inappro-
priate to use the same coating procedures for these materials, and
therefore they are not commonly used in laboratory applications.
The situation changes significantly, when a full-scale case is con-
sidered. In an industrial reactor, the natural choice for coating a
photocatalyst should be on the walls of the reactor or on struc-
tures, specifically designed for the purpose. Metals are generally
the material used for the walls, supporting the entire reactor. Hav-
ing glass or ceramic on the walls, means adding another layer on
the metal, increasing the production costs of the reactor. In case
of structures (e.g. plates or foams), specifically built to support
the photocatalyst, the manufacturing process is much simpler and
more inexpensive if metal is used, since it is easier to shape. Fur-
thermore, metal can withstand the mechanical stresses generated
inside the reactor, ceramic or glass supports may not sustain the
load, resulting in cracks and fractures of the support. For these
reasons, metal is definitely the preferred material in full-scale
applications. However, a catalytic powder is difficult to coat on
metal, due to the particularly smooth surface, and the coating pro-
cess is therefore challenging.
One way to ensure a stable coating is the surface treatment
of metals by corrugation. The treatment produces a very rough
surface, possibly with a positive skewness, enabling a deposit of
the photocatalyst particles in the valleys of the corrugated sur-
face [28]. The photocatalyst particles are then protected from the
mechanical stresses, caused by, for instance, an air stream flow-
ing at high speed on the surface of the support. Several treatments
may be used on metallic materials, such as stainless steel and alu-
minum, to modify the surface. These treatments can be divided
into three main categories: chemical etching, electrochemical DC
(direct current) etching and electrochemical AC (alternate current)
etching. The first category is performed exposing the metallic sur-
face to a solution of an etching agent, normally, an acid. Sulfuric
acid and “H2 SO4 –H2 O2 ” solution (a concentrated solution of H2 SO4
and H2 O2 with a v/v ratio of 2:1, occasionally called “piranha” solu-
tion) have both previously been used to treat stainless steel [29,30].
The treatments proved to greatly increase the roughness of the
sample surface, improving the adhesion of the coated layer. On
the other hand, very few works have been reported for aluminum,
especially using the “H2 SO4 –H2 O2 ” solution. For this material, the
electrochemical DC etching with sulfuric acid of aluminum has
been thoroughly investigated. The process is called anodization
and has been studied for a wide range of applications, mainly
focused on corrosion protection [31]. Recently, a porous surface,
produced by anodization, was used to improve the adhesion of
a coated layer [32]. Giornelli et al. [33] successfully dip-coated a
V2 O5 /TiO2 catalyst on aluminum after anodization. Nevertheless,
it is also important to address how anodization is effective in form-
ing a surface, mechanically stabilizing the catalyst in comparison
to other treatment techniques. Other works investigated the effect
of voltage and temperature on porosity and pore diameter [34,35].
Fewer works, presenting the treatment with DC current of stainless
steel rather than aluminum, are present in the literature. Lee et al.
[36] used aqua regia in DC current, observing a very high restruc-
turing of the steel surface, improving the retention properties of a
lubricant oil. Therefore, we expect that the same treatment could
be successfully implemented to stabilize a photocatalyst coating.
The treatment of aluminum surface has also been investigated
applying an AC current [37–39], while the same treatment has not
been applied, to the best of our knowledge, on stainless steel yet.
In this case, the situation is more complex, since the current can be
either pulsed [37,38] or sinusoidal [39]. In both cases, the treatment
produces cubical terraces on the surface of the aluminum metal,
with a cube size depending on the current frequency [39] and on
the number of applied cycles [37]. Furthermore, Ono and Habazaki
[38] analyzed the effect of H2 SO4 on cubical pits generation and
distribution. However, the work is not directly connected to a coat-
ing application and it is not well defined how the pit properties are
affecting the stability of a photocatalyst coating.
Since there is broad range of treatments applicable on met-
als, the produced surfaces also have a wide range of applications,
e.g. corrosion protection [31], oil retention [36] or improving elec-
trolyte capacity [40]. However, to the best of our knowledge, very
few works have been performed evaluating the effect of surface
restructuring on the mechanical stability of a catalyst coating.
We believe that the improved surface properties, observed to be
beneficial for other applications, could be transferred to coating
applications.
Electrochemical treatments for tailoring photocatalyst metal
supports have not been very well investigated, especially in terms
of how the morphology affects the coating stability and activity
of the photocatalyst. In the present work, we investigated how
various electrochemical treatments modify the surface structure
of photocatalysts supports. Stainless steel and aluminum supports
were considered, since they are more suitable than ceramic ones for
industrial applications. We investigated several treatments, both
novel and adapted from the literature, evaluating the resulting
roughness. Samples showing the highest degree of surface modifi-
cations were selected for coating with the TiO2 -P25 photocatalyst.
The mechanical properties of the resulting metal-catalyst couple
were assessed, evaluating how the obtained support morphology
 F. Montecchio et al. / Applied Surface Science 401 (2017) 283–296
influences the mechanical properties and stability of the coating.
The photocatalytic activity of the most stable coating was investi-
gated and compared to the activity of a photocatalyst coated on
a traditional ceramic support. Furthermore, the influence of the
support surface modifications, due to the electrochemical treat-
ments, on the activity of the coated photocatalyst was analyzed
and assessed.
During the tests of the photocatalytic activity, the model com-
pound acetaldehyde was used to represent VOCs. The emission
of aldehydes, in particular formaldehyde and acetaldehyde, is
very common in industrial processes, making acetaldehyde a suit-
able model compound. Furthermore, this VOC is very toxic, when
inhaled for a long time at low concentrations [45], and odorous,
due to the low odor threshold [11,13]. This makes the investiga-
tion of acetaldehyde especially relevant. Furthermore, compared
to longer aldehydes, alcohols or acids, it is a more stable compound
[46,47], so it is expected that, if the system is capable to oxidize
acetaldehyde, it can oxidize other types of VOCs as well.
2. Experimental
2.1. Materials and methods
The surface treatments in this work were performed on
20 × 20 × 3 mm plates, both commercial 304 stainless steel and
aluminum. Initially, the plates were pretreated with a washing
detergent, followed by deionized water and acetone. After the pre-
treatment, the plates were allowed to dry at room temperature.
This initial step is required to remove surface deposits that may
interfere during the chemical treatments, affecting the results and
the reproducibility of the experiments.
All the treatments were performed in a jacketed glass reactor.
The reaction temperature ranged between −15 and 80 ◦ C and was
controlled by flowing water in the jacket of the reactor through-
out the experiments. The water temperature was controlled with
a thermostatic bath. To homogenize the compounds concentration
and the temperature, the solution was continuously stirred with
a magnetic stirrer. When tests were performed below room tem-
perature, the reactor was immersed in an ice bath (or ice and salt,
when necessary). A large volume of the ice bath, allowed having
stable temperature, with variations of ±2.5 ◦ C around the set point,
during several hours of testing.
After the treatments, all the samples were gently rinsed with
deionized water and dried at room temperature.
2.1.1. Chemical treatments with sulfuric acid
The chemical treatment with sulfuric acid was performed fol-
lowing the procedure described by Giornelli et al. [29]. However,
the cited work presented a treatment for stainless steel, while
we adapted it for use also on aluminum. Each metal plate was
immersed in a solution of 30 wt.% H2 SO4 in deionized water. Dif-
ferent plates of each metal were treated for 2 h at 20 ◦ C and 35 ◦ C,
under continuous stirring, to evaluate the effect of the temperature
on the final surface properties.
2.1.2. Chemical treatments with “H2 SO4 –H2 O2 ” solution
The procedure, presented in the work of Choińska et al. [30],
for the chemical treatments with the “H2 SO4 –H2 O2 ” solution, was
followed. Their work is for treatment of stainless steel only, while
the current work is for treatment of both steel and aluminum. The
solution was prepared mixing 95 wt.% H2 SO4 with 30 wt.% H2 O2
at 2:1 v/v ratio. The untreated plates were immersed for 25 min at
50 ◦ C. The treatment of stainless steel was repeated at 80 ◦ C on a
fresh sample to effectively compare the results with the previous
work [30].
285
2.1.3. Electrochemical DC etching
The electrochemical DC etching on stainless steel and aluminum
was performed following the procedure of Lee et al. [36], applied
by them for the treatment of stainless steel only. The treatment
solution was prepared by slowly adding 1.2% HNO3 to 3.6% HCl at
a v/v ratio of 2:1. The mixing was carried out just before the use
in order to avoid self-decomposition of the acids. A 10.4 cm2 alu-
minum plate was used as a counter electrode. The aluminum and/or
stainless steel to be etched (working electrode) was kept parallel
to the counter electrode at 5 cm distance and then immersed in
the jacketed glass reactor (cell). A constant voltage of 10 V, using
a DC Laboratory power supply (EA-PS 2342-10B), was applied. The
working electrode and counter electrodes were connected to the
positive and negative terminals, respectively. The temperature was
controlled at 25 ◦ C and each metal was etched twice: for 10 or
15 min, producing two samples for each metal.
2.1.4. Anodization
The anodization process was performed for aluminum only, fol-
lowing the work of Giornelli et al. [33]. The pretreatment of the
aluminum plates was modified according to the work of Aerts et al.
[35], including a pretreatment in 1 M NaOH for 60 s at 40 ◦ C, fol-
lowed by an immersion in 1 M HNO3 for 60 s at room temperature
(desmutting treatment). In order to maximize the surface rough-
ness, a low temperature needs to be used [34]. For that reason, the
cell was placed in an ice bath during the course of the treatments.
Afterwards, a 22% H2 SO4 solution was added in the cell. A 26 cm2
aluminum plate, connected to the negative terminal, was used as
a counter electrode, having the working electrode, connected to
the positive terminal, in parallel at a 3 cm distance. The electrodes
were immersed into the cell, applying a current, on the working
electrode, of 1 A dm−2 with a DC Laboratory power supply (EA-PS
2342-10B) for 4 h.
2.1.5. Electrochemical AC etching
The electrochemical AC etching of aluminum was performed
following the work of Ono and Habazaki [38] and, in the present
work, extended to treatment of stainless steel. An acidic solution
containing 2 M HCl and 0.1 M H2 SO4 (1:1 v/v ratio) was used as an
electrolyte. A platinum electrode and a Ag/AgCl·Sat KCl were used
as counter and reference electrodes, respectively. Before etching,
the plate was pretreated in 1 M NaOH at 60 ◦ C for 60 s, followed
by dipping in 1 M HNO3 for 180 s at 60 ◦ C. Before the immersion
in the cell, the sample was gently rinsed with deionized water. A
constant pulse current of 60 mA cm−2 was applied for 1 s using a
Gamry potentiostat. The etching was performed for 100 cycles at
room temperature.
2.2. Morphology characterization
The morphology of the produced surfaces was the first charac-
terization performed after the treatments. A SEM microscope was
used to evaluate the degree of restructuring of the surface. A Zeiss
Gemini Ultra 55 SEM microscope, equipped with an InLens detec-
tor, used for taking the micrographs. The set acceleration voltage
was 10 kV for the aluminum and 5 kV for the stainless steel sam-
ples, respectively. The working distance (WD) was set to 6 mm and
the chosen magnifications were 3k X, 20k X and 100k X.
Additional information about the 3D profile, the volume and the
area of the metallic surfaces, was obtained with an Olympus – LEXT
– Confocal Microscope, equipped with a 408 nm LD Laser.
2.3. Photocatalyst coating
The most promising treated metals, in terms of surface restruc-
turing, were coated with a photocatalyst, to evaluate the stability
286 F. Montecchio et al. / Applied Surface Science 401 (2017) 283–296
of the coating and activity of the catalyst. In parallel to metals, a
ceramic plate was also coated, in order to evaluate mechanical sta-
bility and activity differences due to different support materials.
The photocatalyst chosen is the commercial Evonik P25, since it is
one of the most studied photocatalysts in Literature. Furthermore,
it is inexpensive, making the current study relevant for industrial
applications. The photocatalyst is only composed of TiO2 , present
in two different phases: anastase 75% and rutile 25%. TiO2 -P25 has a
surface area of 50 ± 15 m2 g−1 and a primary particle size of 21 nm.
2.3.1. Coating of treated metallic supports
In the present work, a spraying technique was used for the
coating on metals, without the addition of any adhesive. At first,
the TiO2 powder was dispersed in ethanol with a wt/wt. ratio
TiO2 :EtOH = 1:20. Before coating, the slurry was sonicated for
60 min in order to increase the active surface area by breaking up
the agglomerates of the particles [41]. The sonicated photocatalyst
particles was measured with a Malvern Instruments Zetasizer Nano
ZS to determine the particle size distribution.
The slurry was loaded in a commercial spray painter for the coat-
ing process. The metals were sprayed several time, until at least
50 m2 g−1 of TiO2 were deposited on the surface. Spray coating
is a simple and effective technique, but a precise control of the
amount of coat applied is difficult. Therefore, a final TiO2 -P25 load-
ing between 55 and 80 g/m2 on the supports was reached. This
loading value was chosen to provide a catalyst layer of around
12 ␮m, ensuring a complete adsorption of the UV light irradiat-
ing the surface, as UV light is completely absorbed after 5 ␮m [42].
After each coat, the sample was dried for 30 min at 65 ◦ C before
repeating the procedure.
2.3.2. Coating of ceramic support
The ceramic support plates were made of the mineral mont-
morillonite, a type of clay. The supports are plates of a size of
80 × 80 mm that were roughened with P80 sandpaper beforehand.
The coating was applied on the ceramic support with the dip-
coating technique. TiO2 -P25 was dispersed in an ethanol solution,
with a ratio wt./wt. TiO2 :EtOH = 1:20, and sonicated for 60 min.
The support plate was horizontally immersed in the continuously
stirred slurry at a constant speed, followed by drying at 65 ◦ C for
30 min. The dipping steps were repeated until a TiO2 loading of
at least 50 g m−2 was reached. At last, the sample was calcined at
200 ◦ C for 2 h. This last step is performed to strengthen the bond
between photocatalyst and support. Due to the mild conditions, it
does not change the physical-chemical properties of the photocat-
alyst.
2.4. Test of coating stability
Tape adhesion testing were carried out to determine the
mechanical stability of the TiO2 -P25 coating, according to the stan-
dard ASTM D 3395–09 for X-cut tape tests [43]. Following the
detailed ASTM procedure, a cut of 20 mm length was made on
the surface. A wide, semitransparent pressure-sensitive tape was
applied on the cut, ensuring the complete adhesion of the tape. The
tape was then removed at constant speed and consistent angle,
weighing the coated plates each time before and after applying
the tape. After the tests, the surface uniformity was qualitatively
observed and the amount of coating removed was quantitatively
measured. One single tape test was repeated 12 times for each
sample, until a minor weight difference was observed in the last
repetitions.
2.5. Experimental setup and conditions for activity tests
The most stable coating from the tape test screening was tested
in an UV reactor to evaluate the photocatalyst activity, comparing
with a photocatalyst coated on the ceramic support. The system
was operated under continuous conditions, after achieving steady
state conditions. A detailed description of the used reactor and
experimental setup is reported elsewhere [44].
The reactor is designed to have 80 × 80 mm photocatalytic
plates, while 20 × 20 mm plates were treated and coated in this
work. It was not possible to treat 80 × 80 mm plates directly, since
the current intensity needed for the plate treatments, in some cases,
was very high, higher than the limit of the instruments used. To
respect the design criteria of the reactor, the 16, 20 × 20 mm coated
plates, was glued with silicone to a thin stainless steel sheet, form-
ing an 80 × 80 mm surface, placed afterwards in the reactor. The
ceramic plate support fitted in the reactor without any further
modification, since it was already 80 × 80 mm.
Two tests, dry and humid, were performed for each type of cat-
alyst support, evaluating the photocatalytic activity in terms of
acetaldehyde complete oxidation. This result was calculated mea-
suring the CO2 concentration exiting the UV reactor with an NDIR
instrument (NGA 2000 Rosemount Analytical MLT-1/2-Analyzer).
In all cases, the total air flow rate was set to 7 L min−1 , the VOC con-
centration to 150 ppm and the temperature to 40 ◦ C. The dry tests
were performed without adding water vapor, keeping the humidity
content <1 g Nm−3 , while the humid tests had a relative humidity
of 26%. After the startup of the UV lamps, the conversion was mon-
itored for 2 h, to ensure steady state conditions. The dry test for the
metallic sample lasted for 15 h, to evaluate the evolution of activity
over time.
In order to compare our work with the literature, we calcu-
lated the Turn Over Frequency (TOF), to estimate the acetaldehyde
molecules converted per active site and unit of time, according to
Eq. (1) [48]:
N ∗ SBET ∗ m (TiO2 )
TOF = (1)
Nas ∗ t
where N is the number of acetaldehyde molecules converted in the
unit of time, SBET (m2 g−1 ) is the surface area from the N2 adsorp-
tion, m(TiO2 ) (g) is the mass of the deposited photocatalyst, Nas
(cm−2 ) is the number of active sites and t (s) is the unit of time.
To correlate the activity of the photocatalyst to the surface area,
irradiated by the UV lamps, the “specific surface” was calculated.
This parameter is defined as the ratio between the actual surface
area of the analyzed support and the geometrical area of the same
sample.
3. Results and discussion
3.1. Photocatalyst particle size distribution
Since the electrochemical treatments aimed at modifying the
metal surface, creating a suitable housing for the photocatalyst
particles, it is important to analyze the distribution of the photocat-
alyst powder particle size. Fig. 1 shows the results for the TiO2 -P25
directly after sonication, before application on the support.
The particle size distribution is clearly unimodal, with a well-
defined peak at 148 ± 69 nm. No peaks at larger size were observed,
showing that the sonication step was successful in maximizing the
active surface area and narrowing the particles size distribution
by breaking up large agglomerates. For comparison, the particle
size distribution of the non-sonicated sample is presented in the
Supplementary material, Fig. S6.
 F. Montecchio et al. / Applied Surface Science 401 (2017) 283–296
Fig. 1. Particle size distribution of the sonicated TiO2 -P25 dispersed in ethanol with a wt./wt. ratio TiO2 :EtOH = 1:20.
The electrochemical surface treatments are evaluated consider-
ing the result of the size distribution analysis, since they aimed at
creating catalyst-housing sites with a size between 80 and 500 nm.
3.2. Morphology
In this section, we report on the analysis of the morphological
modifications due to the electrochemical treatments. Only the most
relevant results are reported, while for a complete overview of the
recorded results, the reader is referred to the Supplementary mate-
rial. Indeed, some of the treatments produced a very limited surface
restructuring, while, in some cases, results of different treatments
are similar to those presented in the following section.
3.2.1. Stainless steel
3.2.1.1. Chemical treatments with sulfuric acid. The surface of stain-
less steel is to a very high degree affected by sulfuric acid, due to
a preferential reaction of iron and chromium with the acid, dis-
solving their respective ions [49]. A high restructuring of the whole
surface is expected, due to the high reactivity of the system. These
expectations were confirmed by the SEM micrographs (Fig. 2b).
As shown in Fig. 2b) I, at low magnification, the surface restruc-
turing at the micro-scale level is not very high after treatment at
35 ◦ C. The surface grains are elongated compared to the untreated
sample, but the overall grains pattern is unchanged. This structure
is in line with the results reported in previous works, observing a
stable grains pattern, despite an increase in roughness [29]. A very
different picture is obtained at higher magnifications, presenting
the nano-scale structure (Fig. 2b) II and III). The whole surface of
the grains is affected by the acid, and the surface is much rougher,
compared to the untreated sample. Furthermore, a higher number
of nano-pores and pits are observed. A similar result is observed for
the sample treated at 20 ◦ C with the same technique (Supplemen-
tary material, Fig. S1). Very limited modifications are observed at
low magnification, while a high degree of surface restructuring is
presented at the nano-scale level. However, the surface roughness
is lower, with smaller nano-pores, compared to the sample treated
at 35 ◦ C. This result is in accordance with previous works, show-
ing the relation between the temperature and the etching process
[40,50].
Due to the strong attack of the acid at the nano-scale level, we
expect the treated sample to mechanically stabilize the finer pho-
tocatalyst grains, while larger agglomerates may not be as stable.
3.2.1.2. Electrochemical DC etching. The previous work of Lee et al.
[36] presents a large effect of this treatment on the surface, both at a
287
micro and a nano-scale. A deep and hierarchical surface restructur-
ing is observed also in this work (Fig. 2d). The SEM micrographs are
confirming the results of Lee et al. [36], especially for the hierarchy
of restructuring. A complete and very deep surface restructuring
can be observed already at a very low magnifications, with potholes
of a few ␮m size. Inside these primary potholes, secondary and ter-
tiary nano-potholes can be observed, confirming the high extent of
hierarchy of the treated surface. The same treatment was repeated
for 10 min, instead of 15 min (Supplementary material, Fig. S3), and
a very similar restructuring can be observed, confirming that an
efficient treatment can be reached within a few minutes.
The surface modification at micro-scale caused by this treat-
ment is particularly interesting, especially for powder coating
applications. The size of the potholes is comparable with the size
of the deposited particles, since the tertiary nano-potholes have a
size of about 50 nm (Fig. 2d, III), comparable to the thinner photo-
catalyst particles. Furthermore, the primary potholes, with a size
of about 1 ␮m, can accommodate even the larger titania clusters.
Due to the correspondence between the range of the potholes and
the photocatalyst particles, the treated surface is expected to be a
suitable housing for protecting the particles from eroding agents.
3.2.1.3. Electrochemical AC etching. Since the treatment of alu-
minum with AC in an HCl solution is very effective in restructuring
the surface [38], the same treatment was repeated for the stain-
less steel plates, to check if the procedure could be applicable to a
different metal and verify whether or not similar results could be
observed. Despite some relevant differences, the etching of stain-
less steel has important similarities with the etching of aluminum,
as shown in Fig. 2e. The shape of the pits is spherical, rather than
cubical, as observed with aluminum [37–39]. Furthermore, stain-
less steel is more resistant than aluminum, as shown by localized
pits with smaller sizes, between 100 and 400 nm, and by the con-
servation of the same grain pattern on larger parts of the surface.
Localization of pits is a behavior typical for AC etching, both for
stainless steel and aluminum. Furthermore, the treatment of stain-
less steel exhibits a pit-on-pit propagation mechanism [38], since
larger pits contains several nano-scale secondary pits inside, while
the surrounding surface is not attacked.
Even if pits could be observed in the present sample, the high
amount of untreated surface may affect the suitability of the sample
for a photocatalyst coating. Only fine powder can be coated inside
the pits, while the remaining larger grains have to lay on the flat
sizes of the metal grains.
288 F. Montecchio et al. / Applied Surface Science 401 (2017) 283–296

Fig. 2. SEM micrographs at various magnifications of the stainless steel samples before (a.) and after several chemical treatments. (b.) chemical etching with sulfuric acid at
35 ◦ C. (c.) chemical etching with “H2 SO4 –H2 O2 ” solution at 80 ◦ C. (d.) DC electrochemical etching with diluted aqua regia at 12 V for 15 min. (e.) AC electrochemical etching
with 2 M HCl and 0.1 M H2 SO4 .
 F. Montecchio et al. / Applied Surface Science 401 (2017) 283–296 289

Fig. 3. SEM micrographs at various magnifications of the aluminum samples before (a.) and after several chemical treatments. (b.) chemical etching with sulfuric acid at
20 ◦ C. (c.) chemical etching with sulfuric acid at 35 ◦ C. (d.) chemical etching with “H2 SO4 –H2 O2 ” solution at 50 ◦ C. (e.) anodization at −8 ◦ C and 15 V. (f.) DC electrochemical
etching with diluted aqua regia at 12 V for 15 min. (g.) AC electrochemical treatment with 2 M HCl and 0.1 M H2 SO4 .
290 F. Montecchio et al. / Applied Surface Science 401 (2017) 283–296
3.2.2. Aluminum
3.2.2.1. Chemical treatments with sulfuric acid. When treated with
sulfuric acid, the aluminum supports undergo a similar dissolution
process of stainless steel, but with Al3+ ions dissolved by the acid.
However, there is a considerable difference compared to stainless
steel, whose whole surface is exposed to a general dissolution. In
the aluminum sample, the pit nucleation instead starts in some
particular spots on the metal surface. These spots can be consid-
ered as weak points in correspondence of impurities, as previously
reported by Talbot and Talbot [51]. Starting from these points, the
pit then propagates, until the whole surface is attacked. Evidences
of this mechanism have also been observed in the present work,
especially considering the difference between the sample treated
at 20 ◦ C and 35 ◦ C (Fig. 3b) and c)).
Looking at the micrographs at 20k and 100k magnification
(Fig. 3b) II and III), it is clear that the sample treated at 20 ◦ C has
an intermediate behavior between the untreated sample (Fig. 3a)
II and III) and the one treated at 35 ◦ C (Fig. 3c) II and III). There is,
indeed, a partial restructuring of the surface because the pits nucle-
ated in the weak points and are still expanding. However, there are
still untreated parts of the surface, forming a network geometry
surrounding the pits.
On the other hand, the sample treated at 35 ◦ C presents a com-
pletely restructured surface, related to the increased rate of the
corrosion process at the higher temperature (Fig. 3c). Due to the
acid action, several potholes present at low magnifications (Fig. 3a)
I), were levelled out, resulting in a smoother surface both at a
micro- and nano-scale. Inside the primary pits, the formation of
secondary pits can be observed (Fig. 3c) II and III), with a diameter
of up to 200 nm, subsequent to the propagation of the primary pits
throughout the surface. This phenomenon is due to the increase of
the acidity of the solution during the treatment. The dissolved Al3+
ions reacts with H2 O, leading to the formation of H+ ions that lower
the pH and make the condition more aggressive [52].
Despite the fact that both stainless steel and aluminum undergo
a similar dissolution reaction, the different pit nucleation mecha-
nism affects the morphology of the treated surface significantly.
Stainless steel is restructured only at the nano-scale, with rougher
edges of the grains (Fig. 2b). On the contrary, the restructuring of
aluminum is already observed at the micro-scale (Fig. 3c) I), with
a leveling of the potholes. Higher magnifications show that the
surface is smoothed, rather than roughed (Fig. 3c) II and III).
Since the surface is completely restructured, even at differ-
ent scales and levels, the metal plate obtained with the present
treatment is promising for stabilizing the coated photocatalyst.
However, at the micro-scale, the surface was levelled out by
the acid, potentially compromising the stability of larger powder
agglomerates.
3.2.2.2. Chemical treatments with “H2 SO4 –H2 O2 ”solution. The
behavior of aluminum in sulfuric acid is very different from stain-
less steel, when the acid is very concentrated. Even if aluminum
has a peak in the dissolution rate at intermediate concentrations,
it still has a high dissolution rate even at high sulfuric acid
concentrations [53]. This work confirms a high extent of surface
restructuring (Fig. 3d), since the surface appears to have a high
degree of restructuring already at low magnifications (Fig. 3d) I).
The bumps were levelled out and it is possible to observe clusters
of pits, with a size of 1–2 ␮m. These clusters are even more evident
at higher magnifications (Fig. 3d) II and III), where it becomes
clearer that they are originating from pits that closely nucleate and
successively cluster together. Furthermore, several nano-pores
are observed on the surface with an approximate diameter of
30–50 nm.
Compared to stainless steel, the “H2 SO4 H2 O2 ” treatment has
a completely different effect on aluminum. While stainless steel
is deeply attacked only at intermediate acid concentrations, alu-
minum is restructured also by concentrated acid. Since aluminum
does not undergo the passivation mechanism observed with stain-
less steel, the restructuring of the surface is proportional to the
acid concentration, as proved by the large surface modifications
observed with the “H2 SO4 H2 O2 ” treatment.
Despite the complete surface restructuring, this sample is not
expected to have a high performance as photocatalyst support.
Indeed, the flattening process observed at micro- scale (Fig. 3d) I)
is likely to affect the mechanical stability of the coating, especially
for the larger powder agglomerates.
3.2.2.3. Anodization. The process of aluminum anodization has
been studied for almost one century, since 1923 [54]. In the pres-
ence of an electric current, there is a metal oxidation and water
splitting reaction, responsible for the increase of the surface oxide
layer [55]. This process is responsible for creating a large num-
ber of ordered nano-pores. The first step of their formation is the
nucleation at impurities, dislocation or grain boundaries on the
surface [56]. The pit propagation and pore structure is then depend-
ing on the oxidation rate at a nano-metric scale, causing both a
depth propagation and an increase of pore diameter, resulting in
a cylindrical pore shape [56]. In the present work, a regular pore
arrangement could be observed, as shown in (Fig. 3e), confirming
previous studies [34]. Observing the treated sample at low mag-
nification (Fig. 3e) I), there is a low extent of surface modification.
Even if the grain shape is modified, neither a flattening of the sur-
face, nor a roughness increase is observed. The presence of a high
number of nano-pores, shown in Fig. 3e) III, is in accordance with
previous works [34,55,56]. Furthermore, from a qualitative obser-
vation (Supplementary material, Fig. S4), the average pore diameter
is 14 nm and the average inter-pore distance is 35 nm, in accordance
with Sulka and Parkola [34].
The present sample may be suitable for mechanically stabiliz-
ing the coating, despite the minor restructuring at the micro-scale
(Fig. 3e) I). The high number of regular and cylindrical pores, also
having a regular inter-pore distance, allows the stabilization of a
high amount of catalyst powder, if the diameter of the particles is
very fine.
The anodization process may be further improved, as reported
by Ganley et al. [57], describing how hydro-thermal treatment
increased the surface area of an Al oxide layer by up to 25 m2 g−1 .
3.2.2.4. Electrochemical DC etching. The traditional anodization
process was modified, using an aqua regia solution, based on the
procedure used for stainless steel (Section 2.1.3). The aim of the
novel treatment is the evaluation of the effect a different elec-
trolyte, having chloride and nitrate ions, instead of sulfate. The
sought outcome, using aqua regia, is a surface similar to the one
observed in (Fig. 3e), but rougher, even at a micro-scale level.
However, minor differences are observed, compared to traditional
anodization. No significant changes are observed at the micro-scale
(Fig. 3f) I), since the bumps present in the untreated sample (Fig. 3a)
I) are observed with the same size, shape and number in the treated
sample. The effect of the treatment is more evident at higher magni-
fications (Fig. 3f) II and III), where irregular pores are visible. Unlike
the anodization, the inter-pore distance greatly varies throughout
the surface as well as the diameter of the pores that varies between
20 and 50 nm. Not only the diameter changes significantly, but also
the shape of the pores is more irregular, different from a cylinder
observed in Fig. 3e) III. Considering the surface irregularity, it is not
surprising that some pores are coalescing, forming larger clusters
(Fig. 3f) III). The same treatment was repeated for 10 min instead
of 15 min and a milder pore formation could be observed (Sup-
plementary material, Fig. S5). The number of pores is reduced, as
 F. Montecchio et al. / Applied Surface Science 401 (2017) 283–296
well as the irregularity in the inter-pore distance and pore shape
(Supplementary material, Fig. S5).
As the anodized sample, the present sample is promising for a
coating stabilization, but only if the photocatalyst powder is very
fine, down to the nano-scale level restructuring.
3.2.2.5. Electrochemical AC etching. The treatment with AC in a HCl
solution proved to be very effective in restructuring the aluminum
surface. The work of Dyer and Alwitt [39] showed deep changes
in the surface, with the presence of several “cubes” due to the
presence of alternate current. In this treatment, sulfuric acid has a
key role, since it enhances the pit-on-pit propagation mechanism,
with a significant increase of surface area [38]. This work was able
to reproduce this formation of “cubes”, as shown in (Fig. 3g). The
micrograph at low magnification (Fig. 3g) I) shows that pits nucle-
ates on weak points on the surface, as reported by Ono and Habazaki
[38]. Moreover, inside each large primary pit, several layers of hier-
archical cubical terraces are observed, confirming the mechanism
of pit-on-pit propagation [39]. At higher magnifications (Fig. 3g)
III), it is possible to observe that the formation of cubical terraces
continues down to nano-metric scale, with the smallest terraces
having sizes of several hundred nm. The produced terraces have
very smooth sides and very sharp edges, due to the presence of the
AC current, in line with the results of previous works [37–39].
The aluminum sample, treated with AC, is very promising as a
support for catalyst coating. The hierarchy in the pits pattern, due
to the pit-on-pit propagation, creates a structure capable to accom-
modate both large and fine catalyst grains. However, the large parts
of unmodified surface may affect the total amount of stabilized
coated photocatalyst.
3.2.3. Support selection
The aim of the various surface treatments is to evaluate the sur-
face roughness in relation to their suitability as support for coating
with a photocatalyst. To be a successful support, the treated surface
needs to have a high roughness and cavities capable to contain and
protect particles with the size distribution observed in Fig. 1. Some
of the treated plates did not show any significant restructuring,
and were therefore discarded for the photocatalyst coating and tape
test. Due to the low degree of restructuring and roughness achieved,
the mechanical stability of titania on these samples was expected to
be rather poor, similar as for the untreated samples. When a treated
surface is not deeply restructured, grains with flat sizes are still
present on the surface, contributing to a negative skewness. There-
fore, in a full-scale photocatalytic reactor, the powder is deposited
on the flat, exposed to the continuous air flow. Therefore, it cannot
be protected from the mechanical stresses occurring.
The samples presenting a surface with a higher degree of rough-
ness and with new structures like potholes, cubical terraces or pits
were selected for photocatalyst coating. In total five samples were
selected, as presented in Table 1.
The most promising selected candidate is stainless steel surface
treated by DC etching in aqua regia. Unlike the other cases, where
only part of the surface was attacked, the DC etching restructured
the whole surface, forming large primary potholes. The hierarchi-
cal structure of the sample is probably capable of protecting both
large photocatalyst grains as well as nano-metric powder parti-
cles. Another promising treatment for stainless steel is the chemical
etching with H2 SO4 , which caused a complete restructuring of
the surface at nano-scale, making it much rougher. However, the
absence of changes in the microstructure may constitute a problem,
especially for the mechanical stability of larger TiO2 grains.
Among the selected aluminum samples, only chemical etching
with H2 SO4 was capable of affecting the whole microstructure of
the surface. The surface is, however, flattened, implying a not suit-
able housing for the deposited powder, despite the presence of
291
nano-metric pits. The regularity of the surface structures, obtained
with the electrochemical treatments is particularly interesting. In
particular, the AC etching is promising due to the pit-on-pit prop-
agation, contributing to the enlargement of the primary terraces,
making them suitable for relatively large powder grains. On the
other hand, pores produced with anodization, are very long and
tend to not cluster, keeping a diameter of few nanometers.
3.3. Coating stability – tape test
The tape tests were performed on the same way for all the sam-
ples and repeated until only a photocatalyst loss lower than 1% was
observed in the last repetitions. One single tape test series included
a repetition of twelve times, for each sample. The results are shown
in Fig. 4. For comparison, the tape test was performed also on the
ceramic support that showed a complete removal of the photocat-
alyst after only three repetitions. This result confirms that the tape
test is a very severe technique to evaluate the coating mechani-
cal stability and that all the metallic treated samples improved the
photocatalyst stability, since they lasted for 12 repetitions.
It is clearly visible that the SS 2 sample performs much better
than the other samples, since only 25% of the catalyst is removed.
The reason for its high performance is very likely the hierarchy of
the surface (Fig. 2d). Indeed, starting from a micro-scale point of
view, the surface exhibits large potholes, were the larger titania
grains may lay. The same structure is repeated down to the nano-
scale, with secondary and tertiary potholes suitable for trapping the
smallest photocatalyst particles. On the contrary, the other treated
stainless steel sample, SS 1, shows the lowest performances. In this
case, the photocatalyst is largely removed already from the first
tape test and only 50% of the TiO2 loading was left on the metal,
after four tape tests. The flat surfaces of the microscopic stain-
less steel grains (Fig. 2b) expose the larger powder agglomerates
to high mechanical stresses, caused by the tape test, resulting in a
quick detachment. Only the finer particles were protected by the
rougher nano-scale structure. The same treatment on aluminum,
Al 1 Fig. 4, displays a similar result, with a large drop in TiO2 load-
ing after the first four tape tests. In this case, the quick initial drop
is also related to the loss of larger TiO2 agglomerates due to the
flat surface on the micro-scale, caused by the treatment. The regu-
larity of the structure of the anodized sample (Fig. 3e) is reflected
on the regular removal of TiO2 from the Al 2 sample (Fig. 4), since
each repetition of the tape test, after the first, is removing a consis-
tent amount of photocatalyst. Likely, almost all of the larger TiO2
agglomerates were removed in the first tape test, which is due to the
unchanged surface micro-structure after the treatment. After that,
the nano-metric restructuring causes a mild and gradual photocat-
alyst removal, stabilizing at the second highest TiO2 loading, after
the SS 2 sample. Despite the microscopic hierarchical restructur-
ing of the Al 3 sample (Fig. 3g), the TiO2 removal is high, especially
if compared to the samples SS 2. This is probable due to the large
extent of surface area not affected after the pretreatment. However,
further investigations, including tests with a higher number of AC
cycles, are needed to address this issue.
After the tape tests, it was clear that the sample SS 2 is treated
in the most effective way to achieve a mechanically stable photo-
catalyst coating on the surface (Fig. 4) and it was therefore chosen
for the following photocatalytic activity test.
The laser confocal analysis provides a better understanding of
the surface modifications of the SS 2 sample, in relation with the
stability of the coated photocatalyst. 3D images of the untreated
stainless steel and the SS 2 treated samples were acquired in order
to extend the considerations from the SEM micrograph to a 3D
perspective (Fig. 5).
The 3D surface profile confirms and supports the observations
from the SEM micrographs (Section 3.2.1.2). The treated surface
292 F. Montecchio et al. / Applied Surface Science 401 (2017) 283–296

Table 1
Treatments chosen for the titania coating and following tape tests, with their code and morphology description.

Sample code Material Treatment method Surface morphology

SS 1 Stainless steel Chemical etching H2 SO4 High number of pits at nanoscale and rougher surface
SS 2 Stainless steel Electrochemical DC Etching Hierarchical potholes from micro to nanoscale
Al 1 Aluminum Chemical etching H2 SO4 Several nanoscale pits
Al 2 Aluminum Anodization Cylindrical and ordered nanopores
Al 3 Aluminum Electrochemical AC Localized cubical pits, with pit-on-pit propagation
Etching

Fig. 4. Photocatalyst loading and total removal, during the tape tests for the chosen treated samples.

Fig. 5. Laser confocal 3D surface profile of (a.) the treated SS 2 sample and (b.) the blank stainless steel sample.
 F. Montecchio et al. / Applied Surface Science 401 (2017) 283–296
Fig. 6. Evolution of the CO2 production from the photocatalytic oxidation of acetaldehyde for 15 h. The support for the photocatalyst is the SS 2 treated sample.
Table 2
Surface mean, roughness, skewness and kurtosis for the blank stainless steel and
the treated SS 2 sample.
Mean [␮m] Roughness [␮m] Skewness [−] Kurtosis [−]
Blank 1.63 0.17 −1.34 5.89
SS 2 treated 2.76 0.54 −0.08 3.42
is much rougher than the blank, especially considering that the
treated profile has a 5.3 ␮m surface range, while the untreated pro-
file does not exceed 2 ␮m. Furthermore, the blank profile seems to
have a negative skewness, since most of the profile stays between
1 and 2 ␮m and has few sharp valleys. The calculation of surface
roughness, skewness and kurtosis, based on the work of Hansson
and Hansson [58], provides a quantitative analysis of the qualitative
evaluation from the 3D profile (Table 2).
Analyzing the surface mean values, it is clear that the DC treat-
ment produces a highly restructured the surface, since a higher
surface mean is related to the erosion process forming the potholes
observed in Fig. 2d. As observed with the SEM and 3D laser confocal
analysis, the roughness of the treated sample is greatly increased,
compared to the blank sample. This is confirming the results of the
tape tests, since a hierarchical rougher surface is capable of accom-
modating the photocatalyst powder inside the potholes, protecting
it from the mechanical stress caused by the tape tests.
A positive value of skewness is necessary to avoid that the coated
catalyst is deposited on the top of exposed stainless steel grain
sizes. This is the case of the untreated sample that has flat grains
with sharp inter-grain boundaries. It is to be expected that most
of the catalyst would be deposited on the top of the grains, from
where it would be easily removed during the tape test. On the other
hand, the treated sample exhibits a neutral skewness, meaning
that no sharp peaks or valleys are extensively present. This result
is expected since the restructuring process is completely eroding
the stainless steel grains. Furthermore, the resulting surface has
several layers of potholes, rather than isolated peaks. Even if a posi-
tive skewness would be desired, the surface treatment is improving
the stability of the coated photocatalyst, by removing the flat steel
grains, causing the negative skewness. Furthermore, the presence
293
of both peaks and valleys is expected to effectively host and retain
the powder particles.
Finally, kurtosis has been used to describe the shape of the
peaks and valleys of a surface [59]. When the kurtosis is higher
than 3, the surface profile is called leptokurtic, meaning that the
peaks and valleys are very high and sharp. In the present case,
both the treated and untreated samples have a leptokurtic pro-
file, with the untreated sample having a higher kurtosis and valley
sharpness. Even if kurtosis is not directly related to the mechan-
ical stability of the coating, it provides important considerations
regarding the lifetime of the surface (i.e. the photocatalytic support
in the present case). Higher values of kurtosis expose the surface
to higher mechanical stresses, reducing the fatigue life of the sup-
port [60]. Therefore, the surface structure of the treated sample is
preferred for prolonging the lifetime of the support, since it has a
lower kurtosis, compared to the blank sample.
3.4. Activity tests
The last step, to assess the suitability of the support for scaled-
up applications, is the evaluation of the photocatalytic activity. For
these tests, the selected treatment (SS 2, Table 1) was repeated on
a fresh stainless steel plate. The performance of the new treated
sample was compared with the one of a ceramic plate, often used
as catalyst support in lab experiments. The ceramic plate was pre-
pared according to the procedure presented in Section 2.3.2.
First, the activity of the photocatalyst was tested for 15 h, to eval-
uate the stability of the coating Fig. 6. The geometry of the reactor
used for the test is particularly suitable for checking the mechanical
stability of the coating [44]. The flow has a particular pattern, called
“stagnation-point flow”, where the entering gas reaches the pho-
tocatalyst plate orthogonally and at the center. Then, the flow has
a 90◦ turn and flow radially along the surface, towards the outlet of
the reactor. In correspondence to the stagnation point at the center
of the plate, there is a pressure increase that may constitute the
driving force for the catalyst removal. Therefore, the catalyst could
be removed from the central part, reducing the VOC conversion.
294 F. Montecchio et al. / Applied Surface Science 401 (2017) 283–296
Table 3
Turnover frequency (TOF) calculated for our work and for similar literature systems.
Our work Puddu et al. [26]
TOF × 10−5 (s−1 ) 44,5 19,4
Fig. 7. CO2 production for the SS 2 and ceramic samples, at 0% and 26% of relative
humidity.
The CO2 produced during the photocatalytic oxidation of
acetaldehyde was monitored with a NDIR instrument (Section 2.5),
to evaluate the catalyst activity over time (Fig. 6).
To achieve steady state conditions, the system has a stabilization
time of 200 min, not reported in Fig. 6. After this period, the sys-
tem attained steady state conditions, as expected for a continuous
system, with a constant catalyst activity during the remaining 15 h.
This result contributes to highlight the mechanical stability of the
photocatalyst on the support surface, since an eventual removal of
the TiO2 -P25 photocatalyst would result in a decrease in conversion
over time. The steady state CO2 production was 26.3 ± 0.9 ppm.
Based on the value of CO2 production and on Eq. (1), Section 2.5,
it was possible to calculate the TOF of the system and compare it
with literature systems have a similar configuration [26,48,61]. The
results of the comparison are reported in Table 3.
As presented in Table 3, the TiO2 -P25 photocatalyst of our work
has a quite high TOF, comparable to the other works and outper-
formed only by the work of Thevenet et al. [61]. However, despite
the use of the TOF to describe the activity, it is still affected by other
factors (e.g. UV irradiation and chosen model compound) and it is
not possible to find systems in the literature systems with an equal
configuration for an exact comparison. For instance, considering the
model compound, acetaldehyde is rather stable, compared to other
VOCs [46,47]. We believe that Thevenet et al. obtained such a high
TOF because they were using a less stable VOC. This is confirmed by
the work of Šuligoj et al. [48], that presents two different values of
TOF for two model compounds. However, a detailed analysis of the
TOF, as well as its maximization, is out of the scope of this work,
more oriented towards treatments on the support surface and the
consequent photocatalyst mechanical stabilization.
The next step of the investigation is the comparison between the
performance of the treated stainless steel and the ceramic support.
Two different values of relative humidity were selected, 0% (dry
test) and 26% (humid test) at 40 ◦ C. The results are shown in Fig. 7.
For both of the samples there is a decrease of activity with the
relative humidity. This trend is probably due to the inhibition of
the acetaldehyde adsorption on the catalyst, caused by preferential
adsorption of water vapor on the surface [46]. In any case, the activ-
Thevenet et al. [61] Šuligoj et al. Toluene [48] Šuligoj et al. Formaldehyde [48]
90,2 5,7 2,1
Table 4
Specific surface of the ceramic, blank stainless steel and treated stainless steel
supports.
Ceramic Blank Treated stainless steel
stainless steel
Specific surface [−] 1.37 1.39 2.54
ity of the photocatalyst coated on the SS 2 sample is higher than
the one on the ceramic sample. Therefore, the surface treatment
was not only capable of stabilizing titania on the metal surface,
but also to increase the activity. This is probably due to the par-
ticular structure created by the treatment, generating a higher
surface area, thanks to the hierarchical potholes. Therefore, a higher
amount of photocatalyst could be irradiated by the UV light and
activated. To confirm this hypothesis, the laser confocal analysis
was performed also for the ceramic support, evaluating the “spe-
cific surface” according to Section 2.5. Table 4 reports the results of
the “specific surface” for the ceramic and blank and treated stain-
less steel supports. In the current work, we do not report on the
3D surface profile of the ceramic plate, since it has a smooth and
wavy surface. Due to the high extension of the surface waves, it
was difficult to have a profile representative of the whole surface
and to calculate the surface roughness. However, the profile looked
qualitatively smooth with a low roughness. To have a sample more
representative, a larger portion of the ceramic plate was considered
for the calculation of the specific surface.
The specific surface of the ceramic support is rather low and sim-
ilar as for an untreated stainless steel sample, since the actual area
approaches the geometrical area. On the other hand, the treated
sample has a much higher real surface area, since the real sur-
face area is more than two times higher than the geometrical area.
Therefore, in case of the treated sample, a larger amount of the
deposited photocatalyst could be exposed to the UV light, increas-
ing the number of active sites available for the VOCs oxidation. This
results in a higher acetaldehyde conversion for the treated sample,
compared to the ceramic sample, as shown in Fig. 7.
4. Conclusion
The results of the SEM characterization, tape tests and activity
tests show that the treatment of stainless steel in aqua regia with
direct current is the most successful. As presented, it is possible
to obtain a mechanically very stable photocatalyst coating with a
slight increase in terms of photocatalyst activity, compared to the
sample coated on the ceramic support.
The electrochemical treatments presented in this work can be
divided into three categories: chemical treatments with acids, elec-
trochemical DC as well as AC etching. All treated samples were
characterized with the SEM, evaluating the surface restructuring.
Five samples were selected for the tape tests, due to their larger
change in the surface at the micro- and/or nano-scale. Already at
this point of the work, the was the most promising, due to the
new, highly hierarchically ordered surface structure, not observed
in any of the other samples. The tape tests confirmed the aqua
regia treatment of stainless steel in DC to be the most effective for
stabilizing the photocatalyst coating on metal. After repeating the
test 12 times, the TiO2 loss was stabilized at 25% (Fig. 4), a much
lower value, compared to the other samples. The key feature of
the DC etching of stainless steel is the formation of large potholes,
 F. Montecchio et al. / Applied Surface Science 401 (2017) 283–296
with a size of several ␮m that constitute a suitable housing for the
larger clusters of titania particles. The samples having a partial or
absent restructuring of the microscale failed to protect the clusters
of TiO2 that were removed during the tape tests, causing a high
photocatalyst loss.
The activity of the photocatalyst coated on the chosen treated
metal was tested, and compared with a sample applying the same
photocatalyst coated on a ceramic support, to estimate the effect of
different supports and surface treatments. The treated metal sam-
ple presented a stable constant performance for over 15 h, with a
final activity slightly higher than the sample coated on the ceramic
support. This was the final evaluation step for the chosen electro-
chemical treatment, confirming that it fulfills all the requirements
for a metallic photocatalyst support, ready to be used in scaled-
up industrial reactors. The performance of the sample prepared
with this treatment is much higher than the others, confirming the
importance of the screening presented in this work.
Acknowledgments
This work was carried out within the OdourA project organized
in the Mistra Innovation program. Funding from MISTRA and Cen-
triair is gratefully acknowledged.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.apsusc.2016.12.
233.
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