Bucuresteanu, R.C. et al.

NEW ANTIMICROBIAL STRATEGY USING COMPOSITIONS WITH PHOTOCATALYTIC …

NEW ANTIMICROBIAL STRATEGY USING COMPOSITIONS WITH

PHOTOCATALYTIC PROPERTIES
Bucuresteanu, R.C. 1 , Husch, M. 2 , Ionita, M. 3 , Raditoiu V. 4 , Chihaia V. 5 , Marcu, C. 6 ,
Ditu, L.M .1 , Mihaescu, G. 1
1
University of Bucharest, Faculty of Biology, Microbiology Dept., Bucharest, ROMANIA,
2
Bucharest Technical University of Civil Engineering, Faculty of Building Services
Engineering, Bucharest, ROMANIA, 3 Politehnica University, Faculty of Applied Chemistry and
Materials Science, Bucharest, ROMANIA, 4 National Institute for Research & Development in
Chemistry and Petrochemistry, Bucharest, ROMANIA, 5 Institute of Physical Chemistry “Ilie
Murgulescu”, Romanian Academy, ROMANIA, 6 Dambovita County Emergency Hospital;
Targoviste, ROMANIA
mihai.husch@utcb.ro

DOI 10.25039/x48.2021.OP17

Abstract
The paper describes the studies started by an inter-disciplinary team in finding a disinfection
method using a coating with photocatalytically activated antimicrobial properties by visible
spectrum radiation. An own method of preparation led to the obtaining of a photocatalytic
pigment based on copper-doped titanium dioxide to move the activation spectrum to the visible
range. The preparation method was designed so as to allow transposition into industrial
production. The demonstration and measurement of the photocatalytic effect for certification as
an industrial product was done based on an adapted method, starting from two existing
standards. A washable paint containing the photocatalytic pigment was tested "in situ", the
results demonstrating the reduction of microbial load. The paper is based on current knowledge
about light-activated antimicrobiological agents (LAAs) in an attempt to further the study of
visible spectrum radiation, which in combination with a series of photosensitizers excited by
this radiation, have the role of generating photocatalytic reactions with disinfection effect.

Keywords: Photocatalytic, TiO 2 , Vis desinfection, antimicrobial, HAIs

1. Introduction
The first decades of the 21st century show that we are heading towards a “post-antibiotic” era
[1] characterized by an exponential increase in the number of healthcare associated infections
(HAIs) concomitantly with the emergence of antibiotic-resistant bacterial strains. The entry into
this post-antibiotic era is related to the resurgence of the phenomenon of antibiotic resistance
of pathogens. Pathogenic microorganisms have the ability to physiologically develop a defence
response to the action of physical or chemical stress factors in the environment, a response
that has the role of counteracting the action of these factors. This bacterial physiological
mechanism, defined as a mechanism of antibiotic resistance, is responsible for the occurrence
of drug-resistant pathogens.

The last century was characterized by the intensive use of antibiotics that led to increased
morbidity and mortality caused by pathogens concomitantly with the explosion of HAI cases.
Over the past 40 years, public health budgets have spent large sums on fighting HAI infections
and for treating these super-resistant bacteria. In the United States [2], it has been shown that
implementing proper HAI prevention and control techniques could save human lives and help
saving billions of dollars. The phenomenon is not new [3], it has been identified since the
emergence of penicillin, and Fleming himself, the discoverer of penicillin, in his speech with the
occasion of the Nobel Prize awarding ceremony [4] draws attention to the phenomenon of
antimicrobial resistance caused by irrational consumption of antibiotics. In 1942, Charles H.
Rammelkamp published the first studies on the phenomenon of resistance and identified the
first strains resistant to penicillin [5] [6]. The COVID-19 pandemic during 2020 revealed the
limits of public infection control strategies and prevention mechanisms of the sanitation systems

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[7] highlighting the vulnerabilities of modern society. This pandemic caused a health crisis,
emphasizing the need to ensure clean spaces and surfaces that could allow the development
of medical activities in sanitary-safe conditions.

The coronavirus pandemic required the implementation of certain urgent measures and
accelerated medical research. On a large scale, as a first step in limiting the transmission of
the virus, the use of UV-C type ultraviolet radiation in the 250nm-300nm spectrum has
expanded. This measure, beneficial to a certain extent, is controversial, has a limited effect and
has generated a huge demand for devices with UV-C lamps. The International Commission on
Illumination (CIE) itself has issued a position statement that draws attention, with professional
arguments, to the benefits and also the risks generated by UV-C, and in the USA, the authorities
responsible for preventing and controlling the spread of HAIs do not recommend the use of UV-
C lamps as a first-line defence measure against infectious pathogens. Although UV radiation
has a microbicidal effect, some authors [8] recommend that UV radiation should no longer be
used as a first-line measure for decontamination, but applied as an additional strategy, for
example in conditions of high rates of infection or escalation of infections. When designing and
implementing in the medical area technologies that use as a routine method the
decontamination of UV-C type radiation, several important factors must be taken into account
[8], such as the appearance and design of hospitals, the integration of such technologies in the
management of cleaning and decontamination services, how to install and manage the
operation of UV-C lamps [9], the circuit of patients and medical staff in order to reduce human
exposure to UV-C type radiation. Besides the danger to humans, the use of this UV-C ultraviolet
radiation involves a number of shortcomings that limit their use. UV light is less effective for
places in the corner of walls or in areas protected by solid objects [10]. UV-C light damages
plastics and polymers used in the medical environment if exposed repeatedly. On the other
hand, it must be taken into account that the agents used in cleaning and disinfection substances
[11] can decompose and generate toxic substances for humans, under the influence of UV-C
radiation, as is the case for triclosan or other chlorine-based compounds.

On the other hand, it is known that microorganisms have developed strategies for passive
protection against environmental stress factors by creating bacterial colony structures [12] [13]
called microbial biofilms. The need of bacteria to protect themselves against ultraviolet radiation
[9] [14], dehydration and for the efficient use of food sources was the early evolutionary factor
that led to the formation of biofilms. Recently [15], the idea has emerged that planktonic cells
can only be a transitional lifestyle for bacteria. Biofilm is considered to be the default bacterial
lifestyle. The formation of bacterial biofilm is a universal process that occurs on all environments
to which bacteria can adhere. Biofilms encapsulate bacteria in a matrix consisting of filaments
of extracellular polymeric substances (EPS), filaments synthesized by the bacteria
encapsulated in these structures. Such polymers have the ability to ensure the hydration of
bacteria and to block the action of UV radiations in the environment [9]. The way of organizing
as a matrix which encapsulates the bacteria ensures a "highly effective defensive strategy for
the survival of prokaryotic cells" [14].

Furthermore, microorganisms have developed metabolic mechanisms allowing repair enzymes

and genes to act on DNA when they identify genetic chain damages due to the action of
ultraviolet radiations [16]. These enzymes which are photoreceptor flavoproteins such as LOV,
BLUF and cryptochrome are present in archaea, prokaryotes, bacteria, fungi, animals. They are
configured as UV/blue light systems in the form of flavoprotein light sensors for regulating
phototaxy, DNA repair, stress response and regulating metabolic processes [17].

An example to this effect is the cyanobacteria that evolutionarily preceded the existence of the
existing ozone shield. In order to resist the harmful effects of solar UV radiations, cyanobacteria
developed lines of defence and various tolerance mechanisms: synthesis of absorbent
compounds such as mycosporin (MAA) and scytonemin amino acids, production of antioxidants,
enzymes with the role of DNA repair, protein resynthesis methods, radiations avoidance
methods.

Alcantara-Diaz et al. [18] evaluated the adaptation of E. coli to repeated cycles of sub-lethal
UV-C inactivation at 254 nm. Wild-type E.coli PQ30 cultures were exposed to 80 consecutive
bacterial inactivation by UV-C. In the end, the cultures gave rise to different degrees of
resistance to UV radiations and the existence of a phenomenon of cyclic adaptation to UV

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irradiation was found, as a consequence of the selection of advantageous mutations in different

genes related to DNA repair and replication.

An alarming rise in the number of HAI cases and the emergence of bacterial strains increasingly
resistant to antibiotics have led to an intensification of research to decode the mechanisms of
bacterial defence and the discovery of new strategies to prevent and control HAI [8]. It has been
shown [7] [8] [19] that the effectiveness of any antimicrobial strategy depends on achieving two
objectives: (i) controlling the transmission of microbial aero flora through transport vectors; (ii)
blocking the attachment of planktonic cells to surfaces and preventing the formation of biofilms.

As a direct result of such researches, the following theory was imposed: the permanent action
of passive antimicrobial protection measures reduces the possibility of biofilm formation and is
followed by the decrease of microbial load on contact surfaces [8] [19]. Two observations justify
this theory [20] [21] [22]: (a) resistant biofilms are formed on the intrahospital surfaces, where
the pathogens can survive for a long period of time and will recontaminate the cleaned surfaces;
(b) active methods of disinfection and cleaning are often inefficient for the mechanical and
chemical removal of these biofilms [10]. As a result, the design and construction manner of
medical facilities was rethought in order to obtain an efficient control of air circulation [8], new
generations of protective coating compounds were made [23] and continuous environmental
cleaning and disinfection systems using Blue Light Disinfection technologies [24] [25] [26] [27]
were implemented.

The surfaces of the rooms and furniture in the patient care areas are a reservoir of pathogens
which can easily disseminate pathogens in the environment [8] [10] [20]. The development of
increasingly efficient antimicrobial coatings to protect critical surfaces is an important
desideratum in finding new systems for surface decontamination within medical facilities [10]
[20]. The implementation of the new antimicrobial coatings would also impact on the disinfection
and decontamination costs [28]. To protect these surfaces from being contaminated with
pathogens, antimicrobial coatings have been proposed and applied [8] [10] [20] in the form of
paints or polymeric layers containing biocidal agents. Spreading such coatings over the
surfaces exposed to pathogen contamination directly resulted in a decrease in the transmission
capacity of bacterial germs on such surfaces and implicitly in the number of microbial infections
[11] [20] [21] [29].

As a result of these researches, biocidal compositions have recently been used, in the form of
washable paints in which antimicrobial agents of the 1,2-Benzothiazol-3 (2H)-one type (CAS
no. 2634-33-5), Triclosan (CAS No. 3380-34-5), various polymers, copper or silver are
incorporated [11] [29]. These compositions have proven effective, but there are several
shortcomings that have not allowed these products to be imposed. A major problem with these
products is the phenomenon of sublimation of the biocidal active agent, which leads to a
decrease in the active concentration of the composition mass and, eventually, these
compositions lose their protective properties [12].

The active biotoxic agents in the composition of such protective composites have a very high
level of toxicity, and by their sublimation, toxic vapours emerge and can be inhaled. Numerous
cases of dermato-allergies caused by extended exposure to 1,2-Benzisothiazol-3-one have
been reported [30] [31]. There is a reasonable doubt among the scientific community that
vapours of biotoxic agents found in paints, which are generated by sublimation, are responsible
for increasing the number of nonspecific allergies. Therefore, the European regulatory
authorities wish to limit the use of 1,2-Benzothiazol-3 (2H) -one in various products. Silver has
been used since antiquity as antibacterial product. The new types of silver-polymer composites
are based on the incorporation of silver nanoparticles in different sublayers. It is known that
there is a microbial resistance to silver, especially Gram-negative bacteria, but not Gram-
positive, genetically encoded resistance on chromosomes or in transferable plasmids to other
bacteria [32]. These coatings were not widely spread in the sanitary environment due to
unknown aspects related to emissions and ecotoxicological effects [11]. Unfortunately, there
are no risk-benefit analyses in respect of the use of such biocidal compounds, and the European
regulatory system has many shortcomings regarding the certification of these products, and the
lack of clear evidence of the relationship between benefits and risks can lead to the loss of
potential exhibited by this coating types [8] [13] [21] [22].

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In order to eliminate these shortcomings of the antibacterial coatings of the surfaces,

unconventional antimicrobial strategies that required the need to develop new compounds with
bacteriostatic and bactericidal activity were proposed. We shall set forth hereinafter a new
concept of biocidal agents, which are made out of semiconductor metal oxides and act as light-
activated antimicrobial agents (LAAAs).

At the scientific community level, some communications [33] [34] [35] have brought to the
attention the benefits of visible spectrum radiations, which, in combination with several
photosensitizers aroused by these radiations, generate photocatalytic reactions having a
disinfectant effect [35]. The class of semiconductor metal oxides are the most important
photosensitizers, among which Zinc Oxide ZnO or TiO 2 titaniumoxide. Under the effect of
electromagnetic radiation these oxides release a number of biotoxic, non-selective microbial
active radicals [36]. The photocatalytic method has the key benefit of avoiding problems that
would arise from the induction of antimicrobial resistance phenomena. Several articles
investigated the mode of action of these semiconductor metal oxides, studied the mechanisms
of photocatalysis, and how these mechanisms destroy pathogens [36] [37] [38]. The disinfection
effect of photocatalytic reactions induced by semiconductor metal oxides through
electromagnetic radiation exposure is based on the generation of reactive oxygen species
acting on multiple cellular targets. Microorganisms do not have specific defence mechanisms
against the action of these biotoxic radicals and therefore cannot develop resistance after
repeated exposures. Furthermore, coatings with titanium dioxide or zinc oxide offer both the
possibility of generating reactive oxygen species and a hydrophile surface that is easy to clean.
They form a barrier that opposes the adhesion of microbial cells, having an extended
antimicrobial action, without generating negative effects on the environment [8] [36] [38].

Although these ecological coatings have proven to be promising for reducing microbial load in
medical facilities, they have not been generalized because semiconductor metal oxides are
activated only with UV-A spectral range radiation, in 360 nm - 400 nm spectral band, radiation
that is dangerous to humans. This is why the researchers looked for different methods of
activating these semiconductor metal oxides by visible spectrum radiation. Very good results
were obtained using chemical processes for doping semiconductor metal oxides by metal
impurities in the form of cations of transition metals such as Ag or Cu, Au, Ni, Fe, Cr, Co, Mn.
By such processes, the chemically doped semiconductor metal oxides are activated photo-
catalytically by light irradiation from the spectral range between 450 nm and 500 nm. They can
be used as photocatalytic pigments in the compositions of paints, varnishes or resins, products
that thus acquire antimicrobial photocatalytic properties when activated in visible light.

Unfortunately, so far, all these processes have failed to progress beyond the laboratory stage
and get into production. Based on the known action of light-activated antimicrobial agents
(LAAA), a new concept of antimicrobial and antiviral protection was sought by developing
coatings having self-disinfection properties generated in the presence of light (a concept set
forth in this paper). The article describes the photocatalytic activity of a new model of innovative
paint, which is currently industrially manufactured and certified with photocatalytic antimicrobial
activity in the spectral range of visible light. The paint contains as active substance a micronized
photocatalytic pigment made out of copper-doped titanium oxide. This pigment is activated by
light from the entire visible spectrum thus generating a series of photocatalytic chemical
reactions that result in the emergence of reactive species of singlet oxygen, a toxic product for
bacteria and viruses. Given that the reaction occurs in the area of visible light (Vis), the new
pigment inserted into the paint eliminates the need for photocatalytic arousal with UV-A
radiation. This results in a constant antibacterial protection effect throughout the day under the
action of the sun and during the night under the artificial action of indoor lighting. Compared to
other surface protection compositions, this micronized photocatalytic pigment, made on the
basis of doped titanium oxide, acts as an antimicrobial agent in daylight, is not consumed during
antimicrobial photocatalytic reactions and provides constant protection throughout the life of
the protective film applied to surfaces.

The article sets forth the pigment’s’ chemical characterization, testing and certification of
photocatalytic activity at irradiation with both visible range light and arc-xenon light using an
internal method developed on the basis of the DIN 52980:2008-10 and ISO 10678– 2010
standard, respectively. It also describes the method of photocatalytic antimicrobial certification
according to the industry standards. To study the “in situ” efficiency of this photocatalytic paint,

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it was applied experimentally within the Palliative Care Section of the Targoviste County
Hospital in Romania.

2. Materials and Methods

2.1. Preparation of pigment, as well as of washable paint

Within the small production and testing department of a paint factory, batches of copper-doped
TiO 2 pigments have been manufactured by a sol-gel process. The copper doping concentration
has been calculated at 2%, based on the mass of TiO 2 . The pigment obtained has been used
to produce and homologate at industrial level a washable paint having photocatalytic
antibacterial properties. The obtained product has been approved internally, within the quality
control laboratory of the respective unit, laboratory certified by TÜV Thüringen e.V.

For the obtained paint, the following physical parameters have been measured and obtained.
Density has been determined using the pycnometer method, obtaining an average value of 1.61
g∙cm -3 . Viscosity has been measured by the Brookfield method, using a rotational viscometer,
with rotor 6,20 rpm at 20°C. B value = 14600 has been obtained.

2.2. Evaluation of the UV-Vis absorption spectrum

The light absorption capacity by this pigment has been assessed by UV-Vis spectrophotometric
methods by which the absorption spectra has been made and analyzed both for the pure TiO 2
pigment and for copper-doped pigment. To obtain the spectral curves, a Specord 250
spectrophotometer (Analytic Jena) has been used, using the range 300 nm -1100 nm (Δλ = 2
nm, scanning speed = 10 nm∙s -1 , integration time = 0,2 s). The equipment includes an
integrating sphere as a measuring device in reflectance mode. MgO has been used as a
reference material.

In both samples, we have a strong absorption within the range 330 nm - 370 nm. Pure TiO 2
pigment does not absorb light at all within the visible range. For the copper-doped TiO 2 pigment,
a strong and relatively constant light absorption is observed within the visible range 400 nm -
700 nm.

In order to study the optical properties and light absorption effects, UV-Vis optical absorption
spectra have been raised for the copper-doped anastase TiO 2 pigment, but also for the
photocatalytic antimicrobial paint in which the copper-doped anastase TiO 2 pigment has been
introduced.

Figure 1 – UV-Vis optical absorption spectra of 2% copper-doped TiO 2 pigment

compared to undoped TiO 2

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2.3. Photocatalytic activity test

In order to determine the photocatalytic activity, a sample of photocatalytic antibacterial paint
has been tested as described in this chapter. In the absence of a standard for determining the
photocatalytic activity in the visible spectrum, an own test method developed based on DIN
52980:2008-10 standard “Photocatalytic activity of surfaces - Determination of photocatalytic
activity by degradation of methylene blue”, respectively on ISO 10678 - 2010 “The determination
of photocatalytic activity of surfaces in an aqueous medium by degradation of methylene blue”,
the results of the determinations being presented below.

2.3.1. Description of the testing method:

 Field of application: Method for determining the photocatalytic activity of surfaces by

degradation of methylene blue (MB) in an aqueous solution, under artificial irradiation.
 Specific photocatalytic activity: The measure of the photochemical conversion given in
moles per square meter and hour (mol∙m -2 ∙h -1 ).
 Testing solution: the aqueous solution of MB methylene blue, which serves as a reaction
medium for the determination of surface photoactivity.
 Brief Description: Methylene blue in an aqueous solution has been put in contact with the
active photocatalytic surface of a test sample and irradiated with active ultraviolet or visible
radiation through the dye solution. The dye content of the solution has been determined
successively at well-defined time intervals by UV-Vis spectroscopy. Therefore, the total
specific degradation rate has been determined.
In order to determine the apparent discoloration due to other causes (e.g. by adsorption on
the photocatalytic surface or by photochemical degradation of the dye in the absence of the
photocatalyst), reference measurements have been taken with an active photocatalytic
coating of a test sample in the absence of light, respectively without catalyst in the presence
of irradiation. In the first case, the minimum conditioning time of the photocatalytic paint
samples has been determined until the absorbance of the MB residual solution used for
conditioning was stabilized. In the latter case, the reference measurement was taken in
parallel, in a second vessel, at the same time with the test sample, therefore, the rate of
specific degradation without catalysis could be determined.
 Measuring equipment: quartz cylindrical vessel, respectively borosilicate glass, provided
with magnetic stirring, slide closure lid to prevent water evaporation, support for the plate
with photocatalytic paint; Quartz cuvettes with an optical path length of 10 mm to determine
the MB concentration
 Sources of light: according to the field of interest, put in a closed, parallelepiped enclosure,
made of steel, provided with ventilation. Irradiator with characteristic spectrum, which emits
only in the field of interest, with an irradiation energy E = (15-20) W∙m -2 , measured at the
level of the test sample and in the solution to be analyzed. A Xenotest 150S+ device,
ATLAS, is used for xenon arc lamp irradiation.
 Toolbox: Photoradiometer for measuring the irradiation power of the lamps, calibrated in
accordance with the lamp characteristics and UV / Vis Spectrometer (Jasco UV-Vis-NIR V-
570) for determining the MB concentration, calibrated within the measuring range 400 nm ≤
λ ≤ 800 nm.
 Calibration: The balances, balloons and pipettes used have been calibrated according to
the regulations for monitoring the test equipment.
 Testing and conditioning solution: For testing and conditioning, aqueous MB solutions with
dye concentration are used in the field complying with Lambert-Beer Law. The initial MB
concentration for the test solution must be c 0 = (20 ± 0,1) µmol∙l -1 . The conditioning solution
must have the same concentration c = (20 ± 0,1) µmol∙l -1 . The absorbance A of solutions
has been calculated according to the equation: 𝑨 𝜺 ∙ 𝒄 ∙ 𝒅 , where:

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𝜺 [ l ∙ mol -1
∙ cm -1 ] is the molar absorptivity,
c [ mol∙l -1 ] is the concentration of the solute in solution
𝒅 [ cm ] is the path length of the sample
 Sample preparation: The test sample has a geometric area of (15 ± 1) cm 2 . The substrate
on which the photocatalytic paint was applied has been cleaned according to the
manufacturer's instructions. During the last stage of cleaning, it has been kept under UV
radiation with a wavelength λ < 400 nm and an irradiation power E > 10 W∙m -2 for 24 to 72
hours. For conditioning, two similar test specimens have been placed in containers with
conditioning solution. Both tubes with test specimens and the conditioning solution have
been stored in a dark area, under identical conditions, for at least 2 days. As soon as the
concentration of the conditioning solution was below that of the test solution (A < 1), the
conditioning was repeated with a fresh conditioning solution.
 Taking the measurement: The exposure has been performed using a volume of test solution
V = 45-75 ml of concentration 20 mg∙l -1 of MB in water, a photocatalytic coating surface A =
16 cm 2 , irradiation source depending on the spectral range for which there is evaluated the
photocatalytic activity and a length of the measuring layer d = 10 mm. The amount of test
photocatalytic paint deposited on glass plates was m = 0,07 g, with a thickness of the
deposited layer g = 0,03 mm. The MB test solution has been homogenized by continuous
stirring during the test, using a magnetic stirrer. The test solution temperature (25 ± 1) °C.
 The absorbance measurement has been taken at a wavelength λ = (664 ± 2) nm. The
absorbance has been determined by external measurements of the test solution and then
putting back the measured solutions into the test solution. The absorbance has been
measured at 30 min. intervals, at most until the solution discoloured. The molar absorption
coefficient (MB) is =7402,8 m 2 ∙mol -1 .

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Table 1 – Light sources used to illuminate the test sample: V1 (UV-A), V2 (Vis), V3 (UV-
Vis) and their own spectral characteristics

Source of light / spectral range / Emission spectrum of the used source of

irradiance: light:
V1 UV OSRAM HQE 40W

Emission spectrum:
300 nm ≤ λ ≤ 420 nm

Irradiance E = (20 ± 0,5) W∙m -2

V2 Stairville LED Power-Flood 100W WW

Emission spectrum:
400 nm ≤ λ ≤ 800 nm

Irradiance E = (15 ± 0,5) W∙m -2

V3 Xenon arc lamp ATLAS NXe 2000 HE

with an IR filters system

Emission spectrum:
300 nm ≤ λ ≤ 800 nm

Irradiance E = (42 ± 0,5) W∙m -2

An MB solution with a concentration 20 mg∙l -1 was irradiated with three light sources V1, V2,
V3, whose characteristics are indicated in table 1, in the presence (V1.1, V2.1, V3.1) and in the
absence (V1.2, V2.2, V3.2) of a plate with antibacterial photocatalytic paint, resulting in six test
variants. The six instances of the variation of the absorbance of the MB solution are graphically
represented in table 2.

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Table 2 – Variation of the absorbance of MB solution in the presence (V1.1, V2.1, V3.1)
and in the absence (V1.2, V2.2, V3.2) of the plate with antibacterial photocatalytic paint

Variation of the absorbance of MB solution Variation of the absorbance of MB solution in

in the presence of the plate with the absence of the plate with photocatalytic
photocatalytic paint paint

V1.1 V1.2

V2.1 V2.2

V3.1 V3.2

As a result of the tests performed, the observations regarding the photocatalytic activity are
summarized in table 3.

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Table 3 – Summary of observations in performing the six tests

Instance: Remarks:
V1.1 The discoloration of the aqueous MB solution is linear.
The total specific degradation rate in ultraviolet is R tot = 3,75∙10 -5 mol∙m -2 ∙h -1
V1.2 The discoloration of the aqueous MB solution takes place almost linearly (in a good
approximation).
The specific degradation rate without ultraviolet catalysis is R irr = 0,6∙10 -5 mol∙m -
2 -1
∙h
V2.1 The discoloration of the aqueous solution of MB in the lighting conditions specified
above and in the presence of ALINNA photocatalytic paint takes place in proportion
of 96%, after 3360 min.
There is a linearity range of the decrease of the absorbance of MB solution in terms
of time, a range which, in this case, is up to a discoloration of the solution of 75%
after 1800 min. After this, the process becomes nonlinear, probably due to the
desorption-adsorption diffusion equilibria that control the last part of the process
((1800 – 3360) min. interval).
In order to estimate the photocatalytic activity, only the linear range of the global
discoloration process of MB solution shall be used.
Due to the processes that take place simultaneously (there is the possibility of
overestimating the photocatalytic activity within the visible range).
The total specific degradation rate within the visible range is R tot = 1,57∙10 -5 mol∙m -
2 -1
∙h
V2.2 Discoloration of the aqueous MB solution is a slower process and it is linear.
In order to avoid overestimation, the values of the absorbance differences are
subtracted from those obtained in the case of the global process.
The rate of specific degradation without visible catalysis is R irr = 1,11∙10 -5 mol∙m -
2 -1
∙h
V3.1 The discoloration of the aqueous MB solution takes place linearly on the
considered range.
The total specific degradation rate at xenon arc irradiation is R tot = 0,295∙10 -4
mol∙m -2 ∙h -1 (obtained by reference to an equivalent irradiance of 15 W∙m -2 )
V3.2 The discoloration of the aqueous MB solution takes place linearly on the
considered range.
The specific degradation rate for xenon arc irradiation is R irr = 0,231∙10 -4 mol∙m -
2 -1
∙h (obtained by reference to an equivalent irradiance of 15 W∙m -2 )

2.3.2. Conclusions of the photocatalytic test

ALINNA photocatalytic antibacterial paint sample under analysis shows photocatalytic activity
demonstrated by discoloration of an aqueous solution of Methylene Blue with a concentration
of 20 mg∙l -1 both for irradiation exclusively with light from the proximate UV range and for
irradiation exclusively with light from the visible range, as follows:

 when irradiated with light from the proximate ultraviolet range (300 nm - 400 nm), with an
average specific photocatalytic activity PMB = 3,15∙10 -5 mol∙m -2 ∙h -1 ;
 when irradiated with light from the visible range (400 nm - 800 nm), with an average specific
photocatalytic activity PMB = 0,46∙10 -5 mol∙m -2 ∙h -1 ;
 when irradiated with xenon arc light (300 nm - 800 nm), with an average specific
photocatalytic activity PMB = 0,64 ∙10 -5 mol∙m -2 ∙h -1

2.4. Antimicrobial tests “in situ”

The tests were performed during January 2019 – December 2020, in Targoviste County
Emergency Hospital, Palliative Care Sector, in two types of areas: (i) 2 hospital wards where

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photocalytic activated paint ALINNA was applied and (ii) 2 hospital wards where photocalytic
activated paint ALINNA was not applied.

The total microbial load of indoor air in the two types of in hospital wards was monitored for two
years, following the Standard internal procedure, for monitoring the microbial air load.

There was a significant decrease in the total number of microorganisms in the painted rooms:
from 79 CFU∙m -3 in 2019 to 0 CFU∙m -3 in 2020, compared to the unpainted rooms in which the
total number of microorganism remained relatively constant, from 315 CFU∙m -3 in 2019 to 236
CFU∙m -3 in 2020.

Figure 2 – The evolution of the microbial load of the air in the hospital wards

3. Discussions
The photocatalytic properties of TiO 2 were discovered by Akira Fujishima in the early 1970s
when he observed that TiO 2 facilitates chemical reactions by exposure to light. This discovery,
also called the "Honda-Fujishima effect", was published in a 1972 issue of the journal Nature
and marked the beginning of the era of photocatalysts based on semiconductor metal oxides.
Until the beginning of the 21st century, photocatalyst technology was commercially developed
and used in a variety of products, including self-cleaning tile coverings, street lighting coverings,
and car mirrors. There was also hope that photocatalysts could be used to decompose
environmental pollutants. Unfortunately, a whole series of limitations caused by the specificity
of the photocatalytic activation process of TiO 2 have prevented the emergence of large-scale
products. One of the causes that did not allow the large-scale expansion of TiO 2 photocatalysts
is due to the fact that photoactivation is done with radiation from the near ultraviolet spectral
range, respectively 370 nm, radiation that is dangerous to humans.

This article sets forth the effort of several researchers who set out to move from a photocatalytic
process based on a laboratory model to a model of photocatalytic product transposed on an
industrial scale. The optical properties of light absorption in the UV-Vis range are analysed
using spectrophotometric methods. The absorption curve was raised for the doped TiO 2
pigment, but also for pure, undoped TiO 2 and then the obtained spectra were compared.
Comparing the two spectra, it is to be noted that the pure anatase TiO 2 pigment obtained a
characteristic response in the 360 nm – 400 nm spectral area, while the copper-doped TiO 2
pigment obtained an optical absorption curve over the entire visible 400 nm – 700 nm spectrum,
whose percentage values are high and relatively constant over that range, which indicates that
the activation of the photocatalytic process for this pigment can be done with electromagnetic
radiation from the entire visible spectrum. The analysis of the absorption spectral curve provides
us with valuable information about the photocatalytic process. First, the fact that we have a
relatively constant absorption level over the entire visible spectrum indicates that the intensity
of the photocatalytic process is constant regardless of the type of light (artificial or natural) used
to initiate the photocatalytic reaction. Another aspect noticed in the interpretation of the

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absorption spectra of the doped TiO 2 pigment is the fact that this pigment has on the whole
visible spectrum a high efficiency in generating photocatalytic reactions.

In order to measure the photocatalytic activity, it was decided that the studies be made starting
from an existing method in the industry that can be understood and reproduced in a production
control laboratory by a technological engineer responsible for ensuring the production quality.
The existence of an industry accepted standard (DIN 52980: 2008-10, and ISO 10678 –2010
respectively) determined this approach, as it is suitable for the evaluation and certification of
industrial photocatalytic products. Based on these standards, the method described above was
developed and the photocatalytic activity was compared both in the UV-A range and in the
visible range. The method shows that the copper-doped TiO 2 pigment shows photocatalytic
activity both on irradiation exclusively with light from the near UV range and on irradiation
exclusively with light from the visible range. The average specific photocatalytic activity in
illumination with artificial light in the visible range (400 nm - 800 nm) is equal to the average
specific photocatalytic activity in illumination with xenon arc light (simulating natural light)
predictable result from spectral curve measurements of copper-doped anatase TiO 2 pigment. It
is interesting that the difference between the average specific photocatalytic activity in
illumination exclusively with UV-A, whose value is PMB = 3,15 ∙ 10 -5 mol∙m -2 h -1 , differs only by
an order of magnitude compared to the average specific photocatalytic activity in exclusive
illumination with visible light that has a value of PMB = 0,46 ∙ 10 -5 mol∙m -2 h -1 .

TiO 2 pigments are part of the group of semiconductor metal oxides that are dielectric media in
which there are no free electric charges, only bound and therefore have a dielectric constant
"ɛ" with a high value. In the case of the crystalline TiO 2 pigment, the conduction band (LUMO -
lowest unoccupied molecular orbital) consists of free "3d" orbitals of titanium ions, while the
valence band consists of a pair of non-participating electrons occupying the "2p" orbitals of
oxygen (HOMO - highest occupied molecular orbital). Due to the fact that there are no free
electric charges in the form of conducting electrons, there is an energy difference between the
two bands called the forbidden energy band, and for TiO 2 the value of the forbidden band of 3.2
eV. This energy level corresponds to the close ultraviolet spectral range, with wavelengths of
370 nm, radiation at which TiO 2 is excited and generates a photocatalytic effect.

It is known that, in order to obtain a displacement towards the visible range of radiation
necessary for TiO 2 excitation, transition metals are introduced in the crystalline structure of
TiO 2 which have the role of decreasing the energy interval between the HOMO and LUMO band
of the TiO 2 crystal. The new energy level introduced by the dopant in the TiO 2 network will
capture the excited electrons from the HOMO band of TiO 2 and will allow the photoexcitation of
TiO 2 with electromagnetic radiation from the visible spectrum.

The TiO 2 pigment described in this paper is doped by decorating (depositing) copper
nanoparticles on the crystal surface in the form of copper cation clusters. For catalysts made
from semiconductor metal oxide, including TiO 2 , any catalysed chemical reaction on their
surface is dependent on the concentration of charge carriers on the surface of the catalysts.
When metal particles are deposited on the surface of a semiconductor metal oxide catalyst -
which is a dielectric medium - a new semiconductor dielectric support – metal interface called
Schottky barrier is formed in that area. Formation of the Schottky barrier on the surface of a
semiconductor metal oxide catalyst will generate in that area the change of the concentration
of the charge carriers in the surface layer of the catalyst. This phenomenon that occurs in
Schottky barrier interfaces in catalysts is due to the quantum properties of these metal cations.
Therefore, these nanoparticles that interface with Schottky barriers on the surface of a TiO 2
catalyst will influence and modify the photocatalytic excitation mechanisms.

To understand how photocatalytic excitation mechanisms are influenced by the structure of TiO 2
crystal decorated with copper, it was done by functional density theory (DFT) calculations. The
quantum solid state code CASTEP [39] was used for the DFT calculations, with a high accuracy
spin-polarized calculation scheme (plane-wave ultrasoft pseudopotential, exchange-correlation
functional PBE, energy cutoff of 325 eV, Brillouin zone - discretized by Monkhorst-Pack scheme,
with a spacing of 0,04 Å-1). The quality of the used calculation scheme is validated by the
confirmation of the experimental lattice parameters for anatase and rutile TiO 2 and copper. The
structural model of the copper-doped TiO 2 pigment is given in figure 3.

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The charge density difference was calculated as:

Δρ = ρCu(001)/TiO 2 (001) - (ρCu(001) + ρTiO 2 (001))

where ρCu(001)/TiO2(001) is the electron density of the total Cu(001)/TiO2(001) system, and
ρCu(001) and ρTiO2(001) are the unperturbed electron densities of the two surfaces Cu(001)
and TiO2(001), respectively.

Figure 3 – The charge density difference for the interface TiO 2 (001)-Cu(001) determined
by DFT calculations (original designed). It can be observed that copper forms
coordinative bonds with oxygen at the surface of the TiO 2 crystal and causes an
electron displacement, which would suggest these properties of copper-doped TiO 2 .

DFT calculations have shown us that copper deposits form nanometric clusters on the surface
of the TiO 2 crystal which: (i) generate on the surface of the semiconductor metal oxide crystal
a metal-dielectric semiconductor Schottky barrier interface; (ii) the Schottky barrier thus formed
behaves like an electric dipole characterized by an electric field that performs the delocalization
and degeneration of the HOMO valence orbitals of TiO 2 ; (iii) under the influence of the electric
field of electromagnetic radiation in the visible spectrum, the Schottky barrier formed at the
surface of the TiO 2 crystal will function as a localized surface plasmon (LSP), which will
generate the resonance phenomenon of free electrons in relation to field strength vector
(surface plasmon resonance SPR).

It is known that any chemical reaction that takes place on the surface of a catalyst made of
semiconductor substrate is dependent on the concentration of the charge carriers. The interface
between the surface of the TiO 2 pigment, dielectric material, and nanometre clusters of copper,
electron conducting metals, is a Schottky barrier interface. When metal particles are deposited
on the surface of a dielectric semiconductor catalyst, a metal-dielectric interface is created that
will change the concentration of the charge carriers in the surface layer of the semiconductor.
It is observed that there is a charge density difference that is located in the TiO 2 (001) and Cu
(001) interface area where the Cu atoms form covalent chemical bonds with the oxygen atoms
in the first surface layer of the TiO 2 (001) surface. This charge difference causes a degeneration
of the non-participating 2p electrons of Oxygen, electrons located in the valence band. As a
result of this electronic degeneration, these electrons have a higher energy and can jump more
easily into states of excitation under the influence of an electric field or photon bombardment.
The substrate underlying this effect is given by the property of copper clusters which, in the
presence of the electric field of electromagnetic radiation in the visible range, will function as
surface plasmons capable of generating a localized surface plasmon resonance (LSPR)
phenomenon. due to the plasmonic coupling of electrons with the electric field of
electromagnetic radiation. The high energy level of these degenerate electrons makes it
possible for them to be excited by photons in the visible range and will lead to the occurrence
of excitation states of the pigment, states that will generate photocatalytic reactions in visible
light. The excited pigment crystal has the ability to absorb oxygen molecules from the air at its
surface, and through photocatalytic reactions will yield the excess energy thus forming reactive
singlet oxygen species with the role of destroying bacterial cells.

4. Conclusions

Plasmonic metal nanoparticles can catalyse chemical reactions on their surface when
illuminated by visible radiation. It is shown that these processes are generated by the
phenomenon of localized surface plasmon resonance (LSPR). The interaction of LSPR with
adsorbed orbitals can lead to the injection of charge carriers into the adsorbent with the

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appearance of chemical transformations in the absorbed molecule. The mechanism of the

charge injection process and the role of the LSPR phenomenon are not well understood. Many
researchers have proposed a phenomenon by which localized electric fields induced by LSPR
lead to a direct charge transfer within the molecule-adsorbed system, in the form of injection of
"hot" electrons. There are in-depth discussions on the fundamental phenomena by which the
injection of "hot" electrons is the central point in plasmonic photocatalysis.

We have shown that the interface between metal and dielectric nanoparticles forms Schottky
barriers that will lead to the degeneration of electrons in the valence band. It is possible that
these degenerate electrons become "hot" electrons that will be injected into the processes of
plasmonic photocatalysis. Research is needed to determine how these electrons degenerate
and how they influence photocatalytic reactions.

It is also necessary to implement in the existing standards the possibility of testing

photocatalytic materials under the action of visible light, as a result of the emergence of an
increasing number of photocatalytic products activated by visible light.

Along with similar studies that try to find alternative methods to UV radiation disinfection,
eliminating its limitations and unwanted effects, this research targets the methods of controlling
pathogens, which are environmentally friendly, inexpensive, with continuous action and without
adverse side effects.

The paper draws attention to the fact that together with photocatalytic coatings, radiation from
the entire visible spectrum can play an important role in generating oxidative reactions with a
disinfectant effect on surfaces, the light once again demonstrating its beneficial effects on
human health.

Acknowledgments

We gratefully acknowledge the financial support offered by the research grant no. 527/2020,
project code: PN-III-P2-2.1-PED-2019-1825, UEFISCDI

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