Journal of Photochemistry & Photobiology, A: Chemistry 405 (2021) 112981

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Journal of Photochemistry & Photobiology, A: Chemistry

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

Correction of experimental action spectra for TiO2 photocatalysts measured

using single-peak LEDs
Mikhail Lyulyukin a, b, *, Nikita Kovalevskiy b, Dmitry Selishchev b, Denis Kozlov b
a
Novosibirsk State Technical University, Novosibirsk, 630073, Russia
b
Boreskov Institute of Catalysis, Novosibirsk, 630090, Russia

A R T I C L E I N F O A B S T R A C T

Keywords: In this paper, we show the action spectra for five commercially available TiO2 photocatalysts and a uranyl-
Photocatalytic oxidation modified TiO2 photocatalyst prepared in laboratory. The action spectra are evaluated as spectral dependencies
TiO2 of photonic efficiency in the complete oxidation of acetone vapor under radiations from UV to visible range
Diffuse reflectance
(367–734 nm) provided by seventeen single-peak light-emitting diodes (LEDs) making an assumption of pseudo-
Action spectra
LED
monochromatic type of radiation from these LEDs. A difference between action and absorption spectra of studied
Monochromatic light photocatalysts is considered and discussed. Based on the actual spectral irradiance of certain LED, a correction of
experimental action spectra is proposed to improve their quality and reliability. The data illustrate a noticeable
difference between actual and experimental action spectra obtained using pseudo-monochromatic single-peak
LEDs. The conclusion about correct endpoint for the activation region of studied photocatalysts is made.

1. Introduction
The diffuse reflectance spectroscopy (DRS) in UV- and visible regions
is frequently used to characterize the optical properties of heteroge­
neous photoactive materials and photocatalysts [1–3]. The obtained
DRS spectra are often converted using the Kubelka-Munk function into a
parameter named F(R), which is proportional to the ratio between ab­
sorption and scattering coefficients. This method is used to evaluate the
absorption spectra of the investigated materials on the assumption that
scattering for these materials is constant in the whole range of wave­
lengths [4,5]. DRS technique gives an important information and makes
possible to predict the photoresponse of a heterogeneous system
depending on the radiation spectrum of a light source used for the
excitation of this system.
The absorption of light quanta is a mandatory step for the photore­
action, but it does not guarantee that this reaction occurs. As an
example, the absorption of light quanta by a semiconductor photo­
catalyst may result in the excitation of an electron from the valence band
to the conduction band, but the photogenerated electron and hole would
not be involved in the further interactions with acceptor and donor of
electrons due to their fast recombination, and no photocatalytic reaction
would occur [6]. Additionally, the optical properties of semiconductor
photocatalyst depend on the crystal phase [7], on the presence of
impurities and dopants [8], on the size and geometry of crystallites [9],
and even on the actual temperature of the photocatalyst [10]. This
means that the state of photocatalyst under reaction conditions and
radiation may substantially differs from that one, in which the optical
properties were investigated. Therefore, the actual data on the rela­
tionship between the photoresponse of a heterogeneous system and the
characteristics of light used for its excitation are important. An approach
based on the investigation of the action spectra allows for the collection
of these data.
An action spectrum is a dependence of relative response during the
photoprocess on the wavelength of light affecting this process [11]. The
concept of the action spectrum shows the spectral sensitivity of mate­
rials or processes and plays an important role in various fields of
research that utilize the energy of light. It is actively used for the
analyzation of photobiological data to show bioresponse in different
systems [12], for the investigation of killing mircroorganisms under
exposure to UV light [13], for the characterization of solar cells to show
spectral dependence of photocurrent (i.e., photocurrent action spec­
trum) [14], and for the characterization of the spectral activity of pho­
tocatalysts [15–18]. A comprehensive review of action spectra in
semiconductor photocatalysis can be found in the recently published
paper [19].
A difference between the absorption and action spectra of

* Corresponding author at: Novosibirsk State Technical University, Novosibirsk, 630073, Russia.
E-mail address: lyulyukin@catalysis.ru (M. Lyulyukin).

https://doi.org/10.1016/j.jphotochem.2020.112981
Received 23 June 2020; Received in revised form 8 October 2020; Accepted 12 October 2020
Available online 16 October 2020
1010-6030/© 2020 Elsevier B.V. All rights reserved.
M. Lyulyukin et al.
photocatalysts was previously shown for various processes, namely,
photocatalytic CO2 reduction [20], decomposition of acetic acid [21],
degradation of stearic acid [16], methanol dehydrogenation [17], and
the TiO2-catalyzed photochemical Diels–Alder reaction [22]. Also, the
apparent quantum yield and the action spectrum of certain photo­
catalyst are shown to be dependent on the type of process (e.g. H2
evolution, Ag deposition, decomposition of acetic acid) and the radia­
tion power [7]. Therefore, the use of light absorption properties to
predict the activity of photocatalyst in a certain process is strongly
limited, and the investigation of the action spectrum is important.
Measurement of photocatalyst’s action spectrum requires a lot of
time and many efforts. For this reason, researchers mostly prefer to
compare the activity of photocatalysts with the activity of a well-known
reference sample [23]. TiO2 P25 from Evonik Ind. (Germany), which has
a high activity under UV light and a very low activity under visible light,
is the most commonly used reference sample [24–26]. However, this
approach shows the spectral sensitivity of photocatalyst and is also
affected by the specific spectral characteristics of the light source used
for the excitation of the photocatalyst and reference sample.
In heterogeneous photocatalysis according to IUPAC recommenda­
tions [27], the action spectrum is defined as a plot of a relative chemical
photoresponse per number of incident (not absorbed) photons versus
wavelength (or energy) of radiation used for excitation. Chemical pho­
toresponse per number of incident photons can be evaluated as the ratio
of photoreaction rate to the photon flux of monochromatic light incident
onto the surface of photocatalyst, and this parameter is called the pho­
tonic yield. However, the real light sources are never truly mono­
chromatic, and their emission spectra have a distribution of radiation
power on the wavelength. The width of this distribution depends on the
type of light source and its quality. For example, the typical value of the
peak width, i.e., full width at half maximum (FWHM), in an emission
spectrum of single-peak LED light sources varies from 15 to 75 nm for
different spectral ranges [28–33]. The effect of this width depends on
the type of photocatalyst, but in many cases it is too large to be
considered as monochromatic radiation. In this situation, the term of
photonic efficiency fits better for the correct description of experimental
data, and a more appropriate formulation of experimentally obtained
action spectra is a dependence of photonic efficiency on the wavelength
of incident light (i.e., photonic efficiency spectrum).
Nowadays, modern single-peak or solar-like light-emitting diodes are
frequently used as light sources for photocatalytic processes due to their
safety, high energy efficiency and a potential for practical application
[34–36]. Single-peak LEDs can provide radiation from UV (250 nm) to
near IR (1000 nm) region depending on the type of LED. They have a
single peak on radiation spectrum and can provide a high radiation
power that allows for the fast investigation of action spectra with a high
accuracy. Previously, commercially available KRONOClean 7000 and
P25 photocatalysts were tested in the reaction of NO oxidation using six
LEDs [28]. But a higher number of LEDs with different wavelengths is
required to obtain precise action spectra.
As mentioned above, FWHM in the emission spectrum of single-peak
LEDs may vary from 15 to 75 nm depending on the type of LED. A large
FWHM for certain LEDs may substantially affect the action spectrum.
For this reason, the study aimed at the correction of experimental action
spectra obtained using LEDs to improve their quality and reliability. The
idea of the proposed correction is to use the known spectral photon
distribution for each certain LED for mathematical recalculation and
correction of the experimental spectrum. The action spectra of five
commercial TiO2 photocatalysts, namely, Hombifine N, Hombikat
UV100, Aeroxide P25, KRONOS vlp 7000, and KRONOClean 7000, as
well as a visible-light-sensitive photocatalyst prepared in laboratory via
the modification of TiO2 Hombifine N with uranyl nitrate were inves­
tigated using seventeen LEDs with various positions of emission peak in
the reaction of acetone oxidation. According to the background in
photochemistry, the power of each LED was adjusted to provide the
same value of total photon flux. The correction was performed based on
2
Journal of Photochemistry & Photobiology, A: Chemistry 405 (2021) 112981
the experimental data of spectral irradiance of LEDs and on the data of
photocatalytic activity, and the corrected action spectra of photo­
catalysts were evaluated. The obtained results are discussed and corre­
lated with the optical properties of considered photocatalysts.
2. Experimental
2.1. Materials and characterization of photocatalysts
Five TiO2-based commercial photocatalysts, namely, Hombifine N
from Sachtleben Chemie GmbH (100 % anatase, as,BET = 330 m2 g− 1),
Hombikat UV100 from Sachtleben Chemie GmbH (100 % anatase, as,
2 − 1
BET = 350 m g ), Aeroxide P25 from Evonik Industries AG (rutile/
anatase mixture, as,BET = 55 m2 g− 1), KRONOS vlp 7000 (95 % anatase,
as,BET = 300 m2 g− 1) from KRONOS TITAN GmbH (Germany), and
KRONOClean 7000 (>87.5 % anatase, as,BET = 270 m2 g− 1) from Kronos
Worldwide Inc. (USA) were used as purchased. TiO2 photocatalyst (as,
2 − 1
BET = 300 m g ) modified with 5 wt.% of UO2(NO3)2 via the impreg­
nation of Hombifine N with an aqueous solution of UO2(NO3)2 followed
by drying at 110 ◦ C was also used for evaluation of action spectra. De­
tails of this modification and its influence on the photocatalytic activity
of TiO2 can be found elsewhere [37–40].
The UV–vis diffuse reflectance spectra were recorded using a Cary
300 UV–vis spectrophotometer from Agilent (USA) equipped with a
DRA-30I diffuse reflectance accessory. A pre-packed polytetrafluoro­
ethylene sample from Agilent (USA) was used as a reflectance standard.
The obtained UV–vis spectral data were recalculated into the Kubelka-
Munk coordinates as follows:
(1 − R/100)2
F(R) = (1)
2R/100
where R is the reflectance (%).
2.2. Photocatalytic experiments
The photocatalysts were tested in the oxidation of acetone vapor
under UV and visible light in a continuous-flow set-up, previously
described elsewhere [41], using the following parameters: the temper­
ature of photoreactor is 40 ± 0.1 ◦ C, the volume flow rate is
0.062 ± 0.002 L min− 1; the inlet concentration of acetone is
32–39 μmol L− 1, the relative humidity is 20 ± 1%. An FT801 FT-IR
spectrometer (Simex, Novosibirsk, Russia) equipped with a long-path
gas cell (Infrared Analysis Inc., Anaheim, CA, USA) was used for moni­
toring the products of oxidation. For the experiment, the photocatalyst
was uniformly deposited on a special round plate made from glass. The
geometric surface area for irradiation was ca. 9 cm2. The surface density
of the catalyst on the glass plate was 39 mg cm− 2 for Hombifine N,
37 mg cm− 2 for Hombikat UV100, 21 mg cm− 2 for Aeroxide P25,
27 mg cm− 2 for KRONOS vlp 7000, 31 mg cm− 2 for KRONOClean 7000,
and 29 mg cm− 2 for uranyl-modified Hombifine N, respectively. A high
thickness of catalyst’s layer was provided to absorb the maximum
amount of incident light following IUPAC recommendations [27].
The photocatalytic activity was estimated as the steady-state rate of
CO2 formation, which was the final product of oxidation. The CO2 rate
was calculated from the collected IR spectra using the integral form of
the Beer-Lambert law as the difference between CO2 concentrations in
the inlet and outlet reaction mixtures multiplied by the value of volume
flow rate.
Seventeen single-peak LEDs were used as light sources for irradiation
of catalysts during the photocatalytic oxidation process. The electric
power of each LED was adjusted to provide the same flux of total pho­
tons, (2.35 ± 0.04)×1017 photons s− 1 or 0.390 ± 0.007 μE s− 1 (E is
einstein, i.e. one mole of photons [27]), incident onto the glass plate
with photocatalyst surface. The incident photon flux q0n,p (E s− 1) for each
LED was recalculated from the spectral photon irradiance, measured
M. Lyulyukin et al.
using an ILT 950 spectroradiometer (International Light Technology,
USA), as follows:
∫λ2
q0n,p = S 0
En,p,λ dλ
λ1
where S is the geometric surface area of irradiated photocatalyst (S = 9
cm2), E0n,p,λ is the spectral photon irradiance (E s− 1 cm-2 nm− 1). This
photon flux q0n,p is high enough to achieve the reaction rate data with a
high sensitivity, but not too high for the reaction rate to be in a non-
linear proportion with photon flux [19,42]. The equal amount of inci­
dent photons for various wavelengths allows the correct use of photonic
efficiency term because the normalization to the total number of inci­
dent photons (but not the irradiance) is used. The photonic emission
spectra and the basic wavelengths, which correspond to the maximum of
intensity, are shown in Fig. 1 for all LEDs.
During the test of a photocatalyst, LEDs were changed at the top of
the photoreactor manually in the sequence that corresponds to an in­
crease of radiation energy (i.e., from long-wavelength to short-
wavelength radiation). For each LED, the photonic efficiency of the
process was estimated based on the rate of CO2 formation during
acetone oxidation according to the following equation:
dnCO2 1
ξCO2 = × 0 × 100%
dt qn,p
dnCO2
ξCO2 is the photonic efficiency of CO2 formation (%), dt is the rate of
− 1
CO2 formation (mol s ), is the incident photon flux (E s− 1). The
q0n,p
action spectrum was plotted for each photocatalyst as the dependence of
the photonic efficiency of CO2 formation (%) on the basic wavelength of
the corresponding LED (nm) used as a radiation source.
3. Results and discussion
Using the approach described in the experimental part, we investi­
gate the dependence of the photonic efficiency of CO2 formation during
the photocatalytic oxidation of acetone vapor on the wavelength of the
incident light for several commercial TiO2 photocatalysts. The results of
kinetic experiments are shown in Fig. 2a. The data on activity are pre­
sented along with the light absorption data (Fig. 2b) to compare the
spectral dependence of activity with the absorption spectrum of
photocatalysts.
All the tested samples are TiO2-based photocatalysts with the prev­
alent anatase content. As expected, the photoactivity under light with
wavelengths less than 400 nm is observed for all the samples. The data in
Fig. 2a illustrate that with increasing the wavelength of exciting
Fig. 1. Emission spectra for LEDs used as light sources. Emission spectra pre­
sented for photon flux normalized to (2.35 ± 0.04)×1017 photons s− 1 or
0.390 ± 0.007 μE s− 1.
Journal of Photochemistry & Photobiology, A: Chemistry 405 (2021) 112981
radiation the values of activity for fully anatase TiO2 Hombifine N and
Hombikat UV 100 photocatalysts become zero before all other samples.
Namely, the endpoint of detectable photoactivity for these samples is
observed under LED with the basic wavelength at 460 nm (Table 1). For
(2)
the well-known mixed rutile-anatase P25 photocatalyst [24,26], the
endpoint of activity is achieved under radiation from 500 nm-LED. This
fact can be explained by narrower bandgap for rutile phase of TiO2
compared to anatase.
The KRONOS vlp 7000 and KRONOClean 7000 photocatalysts are
known to absorb visible light due to an organic compound added during
the preparation, which acts as a sensitizer for titania structure [16,43,
44]. As expected, these photocatalysts are active not only under UV, but
also under visible light (Fig. 2a). The detectable photocatalytic activity
during the oxidation process is observed even for LEDs with peaks at 526
and 593 nm for KRONOS vlp 7000 and KRONOClean 7000, respectively.
According to UV–vis spectra (Fig. 2b), absorption of visible light is more
intense for the KRONOClean 7000 sample, but KRONOS vlp 7000 is
more active when irradiated with light of LEDs in the wavelength region
of 403− 526 nm. This result may indicate different origins of the light
absorbance for these samples and, possibly, a difference in the prepa­
ration techniques.
Considering the data of activity and UV–vis spectroscopy data, the
question about the reason for presence of activity for some samples in
that region, where these samples do not absorb light, arises. Indeed,
(3) anatase TiO2, i.e., Hombifine N and Hombikat UV 100 samples, does not
absorb light at a wavelength longer than ca. 400 nm (Fig. 2b), but the
data obtained during the photocatalytic experiments indicate the ac­
tivity for these samples even under LED provided radiation with the
maximum at 450 nm (inset of Fig. 2a). To reveal the reason of this effect,
it is necessary to examine thoroughly the emission spectra of LEDs used
for the photocatalytic experiments (Fig. 1). The wings of peak for each
LED can be seen in emission spectra, and these wings indicate the scopes
of photon distribution. Some photons emitted from LED substantially
differ from the basic wavelength of this LED and may correspond to the
region of higher absorption and higher activity for the considered
photocatalyst. For example, the used LED with basic wavelength of
450 nm provides photons with a wavelength even up to 400 nm (Fig. 1).
This fact distorts the actual value of activity observed under the light
with a wavelength corresponding to the basic wavelength of light for the
used LED.
For a more precise determination of activity under the radiation from
an LED source, it is necessary to consider not only the value of the basic
wavelength, but also the spectral photon distribution for the considered
LED. Therefore, the discrete experimental data points of activity, an,i ,
can be expressed as a function of the actual action spectrum, Aλ , and
spectral photon irradiance of photocatalyst under each LED as follows:
∫λmax
an,i = S 0
Aλ En,p,λ,i dλ (4)
λmin
where an,i (mol s− 1) is the photocatalytic activity detected under ith LED,
λmin and λmax correspond to the edges of irradiance peak for the
considered LED, E0n,p,λ,i (E s− 1 cm− 2 nm− 1) is the spectral photon irradi­
ance of catalyst surface under ith LED, and Aλ (mol E− 1, i.e. dimen­
sionless) is the efficiency of photon utilization.
This approach becomes obvious if we consider a truly mono­
chromatic light source. For this case, the spectral photon irradiance,
E0n,p,λ , turns out into the photon irradiance, E0n,p , and the expression (2)
for photon flux changes to:
q0n,p = S × En,p
0
(5)
Also, the expression (4) transforms into:
0
an = S × Aλ × En,p (6)
3
M. Lyulyukin et al. Journal of Photochemistry & Photobiology, A: Chemistry 405 (2021) 112981

Fig. 2. Spectral photonic efficiency of CO2 formation during acetone oxidation (a) and UV–vis spectra (b) for TiO2 Hombifine N, Hombikat UV100, Aeroxide P25,
KRONOClean 7000, and KRONOS vlp 7000.

longer than 403 nm that well agrees with absorption of light for these
Table 1
samples [1,45]. This value is shown in Table 1 as the recalculated
Endpoints (wavelength in nm) of the activation region for all tested photo­
endpoint of the activation region and means that no activity should be
catalyst samples.
observed for the sample irradiated with monochromatic light of larger
Catalyst Experimental Recalculated wavelength.
endpoint* endpoint
For the mixed anatase-rutile photocatalyst, Aeroxide P25, the
Hombifine N 460 403 recalculated endpoint of activity is 424 nm. This endpoint value
Hombikat UV100 460 403
noticeably differs from the initial value (Table 1) and better correlates to
Aeroxide P25 500 424
KRONOClean 7000 526 526 the UV–vis data. The decrease in photoactivity of Aeroxide P25 with
KRONOS vlp 7000 593 593 increasing wavelength is not as sharp as for anatase samples, and the
Hombifine N modified with 593 512 change in the action spectrum of this sample after correction is not as
UO2(NO3)2 (5 wt.%)
remarkable. However, the observed activity under the light of 450 nm-
*
This value corresponds to the longest wavelength, for which the photo­ LED is nullified after adjustment. The corrected endpoint value for P25
catalytic activity can be experimentally detected. agrees with the bandgap of rutile phase (3.0 eV corresponds to the
wavelength of 415 nm) being in composition of P25 [19,24,45,46].
Another regularity is observed for KRONOClean 7000 and KRONOS
and after simplification with (5), it becomes:
vlp 7000 photocatalysts. No substantial effect of correction was
an = Aλ × q0n,p (7) observed for these samples. For both cases, the activity of samples
gradually decreases as the wavelength of radiation increases. Besides,
which is only a mathematically different representation of expression the recalculated values of the endpoint for action spectra are the same as
(3) used to normalize activity values to the incident photon flux. the initial experimental data. This does not mean that the scopes of
Using the assumptions described above, the recalculation of experi­ activity region remain unchanged. This rather indicates that the values
mental data was performed, and the values of efficiency, Aλ,i , were ob­ of both observed and corrected activity for wavelengths larger than
tained. These values should completely fit the actual action spectra, Aλ , 600 nm are so low, that taking into account the spectrum of the light
and, as a consequence, could be used regardless of the radiation spec­ source does not lead to a detectable change in the endpoint of action
trum of a particular light source. The dependence plot of as-obtained Aλ,i spectrum within the experimental error.
on the basic wavelength of ith LED is to be called as corrected experi­ It is worth noting that the photocatalytic activity of rutile-containing
mental action spectrum (Fig. 3a). A detailed description of the approach P25 photocatalyst is significantly higher in the region of 396− 424 nm
for recalculation of spectral activity data is presented in the SI section. than the activity of organic-sensitized anatase KRONOClean 7000 and
The representation of the action spectra using the recalculated data KRONOS vlp 7000 samples besides the fact of higher absorption of light
(Fig. 3a) illustrates the absence of activity for anatase samples, TiO2 by the latter samples in that region. It indicates higher efficiency for
Hombifine N and Hombikat UV100, under the light with a wavelength utilization of absorbed light quanta in whole photocatalytic process for

4
M. Lyulyukin et al. Journal of Photochemistry & Photobiology, A: Chemistry 405 (2021) 112981

Fig. 3. Corrected action spectra (a) and UV–vis spectra (b) for TiO2 Hombifine N, Hombikat UV100, Aeroxide P25, KRONOClean 7000, and KRONOS vlp 7000.

Fig. 4. Experimental and corrected action spectra (a) and UV–vis spectra (b) for initial (TiO2) and uranyl-modified (5%UO2(NO3)2/TiO2) Hombifine N photocatalyst.

5
M. Lyulyukin et al.
P25 and confirms that the excitation of rutile structure is more efficient
than the generation of charge carriers by the excitation of sensitizers
followed by charge transfer onto the titania.
For an additional illustration of the proposed approach for correction
of action sprectra, TiO2 Hombifine N photocatalyst was modified with
uranyl nitrate to provide the ability for absorption of visible light and
tested in the oxidation of acetone vapor using the same experimental
procedure. The results of these experiments are shown in Fig. 4.
According to UV–vis spectra (Fig. 4b), the presence of uranyl ions on
the surface of titania leads to the appearance of absorption of visible
light in the region up to 530 nm. In addition, the modification of TiO2
with uranyl ions results in the appearance of photocatalytic activity in
the mentioned region. The mechanism of excitation and charge transfer
in the uranyl-modified photocatalyst can be found in our previously
published papers [39,40]. Here, we would consider the action spectrum
of this photocatalyst in details. The experimental dependence of pho­
tonic efficiency of CO2 formation on the wavelength of incident light for
initial and uranyl-modified TiO2 Hombifine N photocatalyst is shown in
Fig. 4a. In contrast to initial TiO2, the uranyl-modified photocatalyst
exhibits a detectable photocatalytic activity in the test oxidation reac­
tion even under LED provided radiation with the maximum at 593 nm.
Also, the local maximum of relative activity is observed at point 424 nm,
which may be attributed to the maximum light absorbance by chem­
isorbed uranyl ions. Under the irradiation of UV light, the observed
activity follows the dependence as for initial Hombifine N, but with a
reduced amplitude. The reduction of activity in the UV region compared
to the activity of initial titania was previously attributed to the trapping
of UV-generated electrons in TiO2 by excited uranyl ions [37].
The representation of the action spectrum for uranyl-modified pho­
tocatalyst using the recalculated data shows more noticeable valley in
action plot near 400 nm if compare with initial experimental data.
Additionally, the actual photonic efficiency at the point of local
maximum (424 nm) is higher than the obtained experimental value. It is
important to note that the second maximum of absorption at 475 nm is
not detected in the action spectrum due to the lack of LED with basic
wavelength close to this maximum. According to data in Table 1, the
endpoint of the activation region for uranyl-modified photocatalyst is
detected at 512 nm that is much shorter compared to the value before
recalculation and more correct. These differences between the recalcu­
lated and experimental plots illustrate the greater sharpness of the actual
action spectrum for the uranyl-modified photocatalyst, and the cor­
rected action spectrum better correlates with the corresponding UV–vis
data for this sample. Therefore, we may conclude that the use of even
narrow-band but not trully monochromatic light sources may cause
blurring of photoresponse spectra and distortion of important data.
The real light sources used for photochemical reactions could radiate
photons with wavelength substantially different from the basic wave­
length. As a result, this may distort the action spectrum of photocatalyst
investigated using these light sources. For example, as shown above, this
effect may cause the red-shift of the endpoint in the action spectra of
titania-based catalysts and significantly distort the shape of the action
spectrum near the local points of maximum and minimum. The results in
this paper show that the experimental action spectra of photocatalysts
should be presented with a reference to the shape of the emission
spectrum provided by the radiation sources.
4. Conclusions
In this study, photocatalytic oxidation of acetone vapor over five
commercially available TiO2 photocatalysts and a uranyl-modified TiO2
photocatalyst prepared in laboratory were studied under UV and visible
light produced by seventeen single-peak light-emitting diodes with basic
wavelengths in the range of 367–734 nm. The action spectra of photo­
catalysts, as spectral dependence of photonic efficiency, were plotted
assuming the pseudo-monochromatic type of radiation from the LEDs.
As the next step, the actual spectral distribution of radiation from each
6
Journal of Photochemistry & Photobiology, A: Chemistry 405 (2021) 112981
LED was measured, and the experimental action spectra were recalcu­
lated and corrected to improve their quality and reliability. Only after
the proposed correction, the experimental action spectra follow the light
absorption spectra of tested photocatalysts, and no activity is observed
for the region with no light absorption. Anatase photocatalysts, TiO2
Hombifine N and Hombikat UV100, and anatase/rutile photocatalyst,
Aeroxide P25, have no activity under a light with wavelengths larger
than 403 and 424 nm, respectively, whereas, visible light photo­
catalysts, KRONOS vlp 7000 and KRONOClean 7000, exhibit the
smoothly falling photoactivity under light up to 600 nm. The modifi­
cation of TiO2 with uranyl ions results in the appearance of light ab­
sorption and photocatalytic activity in the region up to 530 nm. The
action spectrum of uranyl-modified TiO2 photocatalyst well correlates to
the absorption spectrum of this photocatalyst.
For practical purposes, the results obtained illustrate the high
importance of controlling the emission spectrum of the light source used
to initiate photoprocesses, along with the correction of action spectra
using the spectrum of the incident light.
CRediT authorship contribution statement
Mikhail Lyulyukin: Conceptualization, Methodology, Software,
Formal analysis, Data curation, Writing - original draft. Nikita Kova­
levskiy: Data curation, Software, Methodology. Dmitry Selishchev:
Conceptualization, Validation, Writing - review & editing. Denis
Kozlov: Supervision.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
The reported study was funded by RFBR, project number 19-33-
60019. The study was conducted using the equipment of the Center of
Collective Use “National Center of Catalyst Research” at the Boreskov
Institute of Catalysis and was supported by the Ministry of Science and
High Education of the Russian Federation (project АААА-А17-
117041710087-3).
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.jphotochem.2020.
112981.
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