Ceramics International 49 (2023) 30090–30103

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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Using KNbO3 catalyst produced from a simple solid-state synthesis method

in a new piezophotocatalytic ozonation hybrid process
Nicolas Perciani de Moraes a, *, Robson da Silva Souto a, Tiago Moreira Bastos Campos b,
Gilmar Patrocínio Thim b, Yu Lianqing c, Robson da Silva Rocha d, Liana Alvares Rodrigues d, **,
Marcos Roberto de Vasconcelos Lanza a, ***
a
São Carlos Institute of Chemistry, University of São Paulo, Av. Trab. São Carlense, 400 - Parque Arnold Schimidt, São Carlos, SP, 13566-590, Brazil
b
Aeronautics Institute of Technology - ITA/CTA, Praça Mal. Eduardo Gomes 50, CEP 12228-900, São José dos Campos, São Paulo, Brazil
c
School of Materials Science and Engineering, China University of Petroleum, QingDao, 266580, China
d
Lorena School of Engineering- EEL/USP, Estrada Municipal do Campinho S/N, CEP 12602-810, Lorena, São Paulo, Brazil

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

Handling Editor: Dr P. Vincenzini The present work reports the development and application of potassium niobate (KNbO3) as a catalyst in a novel
hybrid piezophotocatalytic ozonation process aimed at wastewater remediation. Pure KNbO3 samples were
Keywords: produced through a simple solid-state synthesis using water-soluble ammonium niobate (V) oxalate hydrate
Piezophotocatalytic ozonation (C4H4NNbO9⋅xH2O) as niobium source, employing different potassium precursors (KNO3, K2CO3, KOH, and
Potassium niobate
C8H5KO4). The synthesis was also carried out using powdered niobium oxide as a precursor, aiming to evaluate
Ammonium niobate (V) oxalate hydrate
the differences between the niobates obtained. The results achieved in this study show that all the niobates
Advanced oxidation processes
produced using ammonium niobate (V) oxalate hydrate were composed solely of the orthorhombic structure of
KNbO3, while the materials synthesized using niobium oxide exhibited the rhombohedral structure of KNbO3
along with niobium-rich potassium niobates (K3Nb8O21, K2Nb4O21, and KNb3O8) and residual niobium oxide.
This behavior was attributed to the enhanced chemical homogeneity derived from the synthesis using ammo­
nium niobate (V) oxalate hydrate, which facilitated the reaction between the components during the thermal
treatment step. Furthermore, the optical and morphological properties of the niobates were considerably
influenced by the application of different potassium salts. Owing largely to its morphological and electrical
properties, the material synthesized using potassium hydrogen phthalate displayed the highest photocatalytic
activity in terms of methylene blue discoloration among the niobates produced using C4H4NNbO9⋅xH2O. Finally,
the proposed piezophotocatalytic ozonation process was found to be a highly efficient strategy for the discol­
oration of methylene blue, as it successfully harnessed the synergy between the multiple mechanisms involving
active radical generation toward the development of a highly promising hybrid advanced oxidation process.

1. Introduction industrial wastewaters. Among these AOPs, the following processes are
considered to be highly efficient remediation techniques: heterogeneous
Over the past few years, the contamination of water bodies by in­ photocatalysis, piezocatalysis, and ozonation [3–7].
dustrial residues has raised serious concerns in the scientific community The principle behind heterogeneous photocatalysis involves the
due to the potentially harmful effects of these contaminants on world­ application of an external light source to excite a photocatalyst, resulting
wide ecosystems [1,2]. Efforts aimed at tackling this global environ­ in the transference of electrons from the valence band of the photo­
mental problem led to the development of advanced oxidation processes catalyst to its conduction band, thus enabling the formation of the so-
(AOPs), which are regarded as highly promising techniques that are called electron/hole pairs. These photogenerated charges will then
capable of helping in the effective remediation of contaminated give rise to the formation of active species, such as hydroxyl and

* Corresponding author.
** Corresponding author.
*** Corresponding author.
E-mail addresses: [email protected] (N.P. de Moraes), [email protected] (L.A. Rodrigues), [email protected] (M.R.V. Lanza).

https://doi.org/10.1016/j.ceramint.2023.06.265
Received 28 February 2023; Received in revised form 22 June 2023; Accepted 27 June 2023
Available online 29 June 2023
0272-8842/© 2023 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
N.P. de Moraes et al. Ceramics International 49 (2023) 30090–30103

superoxide radicals, which can cause the degradation organic molecules potassium nitrate, potassium hydroxide, and potassium hydrogen
in an aqueous environment [8,9]. Piezocatalysis, on the other hand, phthalate) on the performance of the synthesized potassium niobate
employs mechanical vibration to create active species on the opposing catalysts in an attempt to further enhance the efficiency of the piezo­
surfaces of a piezoelectric semiconductor. This effect is derived from the photocatalytic ozonation process.
formation of a built-in electric field which enables the separation of free
electron-hole pairs and the consequent formation of active radicals [10, 2. Materials and methods
11]. Finally, the remediation of effluents through ozonation relies on the
ability of the ozone molecule to promote oxidation reactions with a wide 2.1. Synthesis of the KNbO3 samples
range of organic and inorganic pollutants, directly or indirectly (through
the formation of hydroxyl radicals) [12–14]. Potassium niobates were produced via the application of a simple
Numerous studies reported in the literature have succesfully applied solid-state synthesis procedure, without any pre-treatment step, using
the aforementioned processes for the treatment of the most diverse the correct stoichiometric values for all precursors. Ammonium niobate
range of effluents with promising results [8–14]. The combined appli­ (V) oxalate hydrate and niobium oxide (Nb2O5) were used as niobium
cation of these AOPs in the form of hybrid processes, such as photo­ sources, along with different potassium precursors.
catalytic ozonation, piezocatalytic ozonation, and piezophotocatalysis, Using ammonium niobate (V) oxalate hydrate as a niobium source,
has also been found to successfully harness the synergy between the the materials were prepared as follows: 0.056 mol of ammonium niobate
individual processes, leading to the development of new treatment (V) oxalate hydrate (C4H4NNbO9⋅xH2O), pre-defined amounts of po­
techniques with superior efficiency [15–18]. While most of these pro­ tassium precursor (0.028 mol of potassium carbonate (K2CO3), 0.056
cesses have been extensively explored, to the best of our knowledge, mol of potassium nitrate (KNO3), 0.056 mol of potassium hydroxide
there have been no reports in the literature regarding the combined (KOH) or 0.056 mol of potassium hydrogen phthalate (C8H5KO4)), and
application of the three processes mentioned above, in the form of a 5 mL of deionized water were added to a crucible. The system was mixed
piezophotocatalytic ozonation process. Essentially, the novelty of the until all components were solubilized. The crucible, along with the
present work lies in the development and application of this ternary materials in it, was placed in a muffle furnace and calcined at 600 ◦ C for
remediation technique. 2 h. The materials were named NbOxa-P, where P stands for the po­
Considering the aforementioned piezophotocatalytic ozonation tassium precursor used in the synthesis.
process, potassium niobate (KNbO3) can be employed as an efficient Regarding the synthesis of niobium oxide, the following route was
catalyst. In optical terms, this semiconductor has a large nonlinear op­ adopted: 0.038 mol of niobium oxide (Nb2O5, CAS Nº 1313-96-8, 99%
tical coefficient, excellent optical refraction performance, and good w/w), pre-defined amounts of potassium precursor (0.038 mol of po­
photocatalytic properties under ultraviolet light, with a bandgap energy tassium carbonate (K2CO3), 0.076 mol of potassium nitrate (KNO3),
of 3.2 eV [19–21]. In addition, the orthorhombic, tetragonal, and 0.076 mol of potassium hydroxide (KOH) or 0.076 mol of potassium
rhombohedral structures of KNbO3 exhibit perovskite-type characteris­ hydrogen phthalate (C8H5KO4)), and 5 mL of deionized water were
tics with ferroelectric and piezoelectric properties; all these features and added to a crucible. The mixture was ground until a homogeneous paste
its lead-free structure, in particular, make KNbO3 an environmentally was obtained. The crucible, along with the materials in it, was placed in
safe piezocatalyst [22–24]. a muffle furnace and calcined at 600 ◦ C for 2 h. The materials were
As for the synthesis of KNbO3, the application of simple solid-state named Nb2O5–P, where P stands for the potassium precursor used in the
methods comes with certain underlying challenges; this is primarily synthesis.
because non-stoichiometric stable products with non-unitary K/Nb ra­
tios have the propensity to occur naturally, especially when solid 2.2. Characterization
niobium oxide is used as a source of niobium [21]. This behavior stems
from the inherent low chemical homogeneity between the niobium and The characterization of the materials was performed using the
potassium precursors during the solid-state synthesis, which largely following techniques.
depends on the efficient diffusion of potassium-based precursors into
niobium oxide particles. In view of that, most of the recently reported a) X-ray diffractometry: This analysis was carried out using an Empy­
synthesis techniques of the KNbO3 are based on more complex meth­ rean Alpha-1 diffractometer (CuKα). The Rietveld refinement pro­
odologies - mainly hydrothermal routes and Pechini reactions, which are cedure was used to determine the mass fraction of each crystalline
targeted at enhancing the chemical homogeneity of the K and Nb pre­ component; this analysis was conducted using the Profex software
cursor components during the formation of potassium niobate [21, [32];
25–30]. However, it should be noted that both of these synthesis path­ b) Raman spectrometry: This analysis was performed using a LabRAM
ways rely on very specific equipment and/or reactants to obtain the HR Evolution Raman Spectrometer with an argon ion laser. The
desired KNbO3, usually resulting in costly and time-consuming pro­ spectra were recorded in the range of 150 and 1200 cm− 1, with
cesses [31]. acquisition time of 60 s per cycle;
Thus, the present work aims to develop a new piezophotocatalytic c) Scanning electron microscopy: This analysis was performed using a
ozonation hybrid process through the application of potassium niobate Tescan Mira 3 microscope equipped with a field emission gun (FEG-
(KNbO3) as a catalyst. In this study, KNbO3 is produced through a simple SEM), operating in the secondary electron mode;
solid-state synthesis pathway using a water-soluble niobium precursor: d) Diffuse reflectance spectroscopy: This analysis was performed using
ammonium niobate (V) oxalate hydrate (C4H4NNbO9⋅xH2O). It is ex­ the Shimadzu UV-2600 spectrophotometer, which was equipped
pected that the use of this niobium source, combined with an also water- with an ISR-2600 integrating sphere;
soluble potassium precursor, will generate sufficient chemical homo­ e) Specific surface area analysis: The specific surface area of each ma­
geneity after the evaporation of the water content during the thermal terial was analyzed using a V-Sorb 2800P analyzer (Gold App)
treatment step. Furthermore, this work will also compare the proposed through the application of the Brunauer-Emmett-Teller (BET)
synthesis pathway with an equivalent synthesis mechanism using solid method.
Nb2O5 as a niobium precursor; this comparative analysis seeks to prove f) Electrochemical tests: Chronoamperomtry and open-circuit potential
that the application of the ammonium niobate (V) oxalate hydrate tests were conducted using an Autolab Metrohm potentiostat
indeed facilitates the formation of stoichiometric KNbO3. Finally, a PGSTAT204. A layer of material was deposited on an RDE working
thorough characterization will also be conducted in order to evaluate electrode (Pine Research, AFE3T050PTPK), which was employed
the effects of different potassium precursors (potassium carbonate, along with a Pt foil counter electrode and an Ag/AgCl reference

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electrode. In the experiments, a quartz electrochemical cell with a on the discoloration of MB. To that end, isopropanol (5% v/v) was used
volume of 0.2 L was utilized, which contained an aqueous solution of as a hydroxyl radical scavenger, while benzoquinone (1 mmol) was used
K2SO4 electrolyte at a concentration of 0.1 mol L− 1. The electro­ as a superoxide scavenger [34,35].
chemical system was operated at a potential of 0.8 V (vs. Ag/AgCl).
g) X-ray photoelectron spectroscopy (XPS): The samples were analyzed 3. Results and discussion
using a ScientaOmicron ESCA + spectrometer, equipped with a high-
performance hemispheric analyzer (EAC2000). The XPS measure­ 3.1. Characterization
ments were conducted using monochromatic Al Kα radiation (hν =
1486.6 eV) as the excitation source. The analysis took place in an Fig. 2 shows the X-ray diffractograms obtained for the synthesized
ultra-high vacuum chamber with an operating pressure of approxi­ potassium niobates, along with the Rietveld refinement results.
mately 10− 9 Pa. High-resolution XPS spectra were acquired with a First, regarding the materials produced using ammonium niobate (V)
constant pass energy of 30 eV and a step size of 0.05 eV per data oxalate hydrate as the niobium source, the XRD data show that the
point. To mitigate surface charging effects, a charge neutralizer orthorhombic structure of KNbO3 is present in all the samples, regard­
(CN10) was employed. less of the potassium precursor employed in the synthesis [36].
Furthermore, no other crystalline phase is observed in the diffracto­
grams of these materials; this points to the high purity of KNbO3 ob­
2.3. Evaluation of the piezophotocatalytic ozonation process
tained from the application of C4H4NNbO9⋅xH2O. The mechanism
involving the formation of KNbO3 in the synthesis route proposed is
Fig. 1 shows a scheme of the reactor used in the proposed advanced
based on the decomposition of ammonium niobate (V) oxalate hydrate
oxidation processes.
into anhydrous niobium oxide at temperatures higher than 560 ◦ C and
The advanced oxidation processes were performed using methylene
the subsequent reaction of the oxide with K2O obtained from the
blue (MB) as a model molecule. To that intention, 500 mL of 10 mg L− 1
decomposition of the potassium precursors employed in the synthesis
methylene blue aqueous solution was used in each test. The full
[37–40]. Considering the synthesis proposed and the fact that
assessment of the role of each AOP in the discoloration of MB was car­
C4H4NNbO9⋅xH2O and all potassium precursors employed are water
ried out using the following processes: direct photolysis, ozonation,
soluble, it is expected that the co-precipitation of the reactants after the
ultrasonication, photo-ozonation, photo-ultrasonication, ozonation-
water evaporation will lead to a higher chemical homogeneity of the
ultrasonication, photo-ozonation-ultrasonication, heterogeneous pho­
reaction system. Thus, in essence, the synthesis proposed is expected to
tocatalysis, catalytic ozonation, piezocatalysis, photocatalytic ozona­
facilitate the diffusion process between the oxides, resulting in the
tion, piezophotocatalysis, piezocatalytic ozonation, and
successful formation of potassium niobates, as observed.
piezophotocatalytic ozonation. The OsramPuritec 11W lamp and the
Regarding the materials synthesized using Nb2O5 as a niobium
VibraCell VC 375 ultrasound probe (20 kHz frequency, Sonics & Mate­
source, the first noticeable difference lies in the crystalline structure of
rials Inc) were used as the ultraviolet light and ultrasound sources,
the obtained KNbO3. In all cases, the rhombohedral structure of the
respectively. An AZ-1000MG-G ozonator was used as the ozone source,
potassium niobate was observable in the samples; this can be noted by
with an ozone production rate of 1000 mg h− 1.
the absence of divided peaks in the diffractograms [36]. Furthermore, it
The processes which involved the application of KNbO3 as a het­
is evident that the potassium niobates obtained through this synthesis
erogeneous catalyst were performed with a dosage of 0.2 g L− 1 for the
route were not pure, as several other crystalline phases were observed in
selected material. Furthermore, prior to the tests, the system was kept
the diffractograms of the samples, which were mainly represented by
solely under magnetic stirring until the adsorption-desorption equilib­
unreacted Nb2O5 and other niobium-rich potassium niobates, such as
rium between KNbO3 and MB was observed. The concentration of MB
K3Nb8O21, K2Nb4O21, and KNb3O8. This behavior may be attributed to
was estimated using a Shimadzu UV-2600 spectrophotometer set at 673
the difficulty in the diffusion of the potassium oxide formed during
nm [33]. Aliquots were collected at regular time intervals and filtered
thermal treatment through the powdered niobium oxide particles, as in
through a nylon syringe filter before the measurements. It is worth
this case, the agglomeration of Nb2O5 particles probably gave rise to
pointing out that the tests performed without ultrasonication were
regions with different compositions due to the decrease of the niobium
carried out under magnetic stirring. The scavenger tests were performed
oxide exposed surface. Thus, this disadvantageous characteristic of the
using specific quenchers in order to evaluate the effect of active radicals
synthesis pathway led to the formation of non-stoichiometric potassium
niobates and unreacted niobium oxide, probably in the inner regions of
the Nb2O5 agglomerates.
Table 1 shows the cell parameters and apparent crystallite sizes (Lc)
obtained from the Rietveld refinement analysis conducted for the KNbO3
phase present in the materials synthesized.
Table 1 shows that the Rietveld refinement analysis performed
resulted in a fairly good fitting for the XRD experimental data, as the
values of χ2 are close to 1. The lattice parameters calculated for each
sample were in line with the theoretical values previously reported in
the literature; this shows that there was no major crystalline lattice
distortion for the materials synthesized in this study. As for the apparent
crystallite size of the KNbO3 phase, the results showed that the materials
synthesized using ammonium niobate (V) oxalate hydrate exhibited
crystallites that were relatively larger than the ones observed for the
material synthesized using Nb2O5; this shows that the synthesis pathway
based on the application of C4H4NNbO9⋅xH2O resulted in potassium
niobates with higher crystallinity.
Fig. 3 shows the scanning electron micrographs of the materials
synthesized using ammonium niobate (V) oxalate hydrate as a niobium
Fig. 1. Schematic representation of the reactor used in the advanced oxida­ source, while Fig. 4 shows the micrographs of the materials synthesized
tion processes. using niobium oxide.

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Fig. 2. X-ray diffraction results obtained for the synthesized potassium niobates.

heat treatment procedure. Finally, the results obtained from the

Table 1
morphological characterization of the Nb2O5–KNO3 showed that the
Parameters obtained for the KNbO3 phase in each material based on the appli­
material displays stacked plate-like particles, while the Nb2O5–C8H5KO4
cation of the Rietveld refinement method.
exhibits cuboid-like particles similar to those observed for the materials
Material a (nm) b (nm) c (nm) Lc (nm) χ2 synthesized using C4H4NNbO9 ⋅ xH2O; this behavior may be attributed
NbOxa-K2CO3 0.3981 0.5700 0.5722 107.50 1.84 to the fact that the Nb2O5–C8H5KO4 presents relatively higher KNbO3
NbOxa-KNO3 0.3982 0.5698 0.5719 117.40 2.85 mass fraction compared to the other materials synthesized using
NbOxa-KOH 0.3979 0.5696 0.5715 136.50 1.83
niobium oxide.
NbOxa-C8H5KO4 0.3990 0.5697 0.5714 134.80 2.30
Nb2O5–K2CO3 0.4021 0.4021 0.4021 42.40 2.11 Table 2 shows the results obtained for the specific surface area of
Nb2O5–KNO3 0.4016 0.4016 0.4016 32.44 1.75 each material.
Nb2O5–KOH 0.4018 0.4018 0.4018 44.66 2.30 As can be observed in Table 2, the application of different potassium
Nb2O5–C8H5KO4 0.4019 0.4019 0.4019 43.90 2.27
precursors during the synthesis of the potassium niobates exerted a
significant effect on the specific surface area of the samples. For both
Fig. 3 shows that all the materials synthesized using niobium sources proposed in this study, the synthesis performed using
C4H4NNbO9⋅xH2O are characterized by well-defined cuboid-like parti­ KNO3 gave rise to materials with lower specific surface areas. Regarding
cles. In the case of KNbO3, this is a characteristic behavior that has been the C4H4NNbO9⋅xH2O-based materials, NbOxa-KOH exhibited a rela­
reported previously for materials synthesized through a wide range of tively higher surface area, which was expected due to the crevices pre­
synthesis routes, including hydrothermal, solid-state, and Pechini routes sent in the scanning electron micrographs of the material (Fig. 3-C). As
[22,23,27,41,42]. The use of K2CO3, KNO3, and C8H5KO4 as potassium for the materials synthesized using Nb2O5, Nb2O5–K2CO3 exhibited the
precursors led to the formation of particles with smooth edges and highest surface area; this may be attributed to the presence of small
surfaces, with the NbOxa-K2CO3 material presenting larger particles particles observed in its scanning electron micrographs (Fig. 4-A).
than its counterparts. On the other hand, the material synthesized using Fig. 5 shows the Raman spectra of the materials synthesized in this
the KOH precursor was characterized by smaller particles with very study; this analysis was conducted in order to further assess the struc­
sharp edges and surface crevices. In this sense, it is clear that the use of tural properties of the synthesized potassium niobates.
different potassium precursors during the proposed synthesis of potas­ The Raman spectra of all the samples investigated show the char­
sium niobate results in the formation of materials with different acteristic modes of KNbO3: B1(TO2) (190 cm− 1), B1(TO1) (245.3 cm− 1),
morphological characteristics. B1(TO4) (275 cm− 1), A1(TO1) (296 cm− 1), B1(TO3)(531 cm− 1), A1(TO3)
As for the materials synthesized using niobium oxide, Fig. 4 shows (598 cm− 1), and A1(LO3) (832 cm− 1) [24]. One will notice that the
that the use of different potassium precursors led to significant differ­ resolution of the Raman spectra obtained for the materials synthesized
ences in the overall morphology of the resulting niobates. First, the using Nb2O5 is relatively lower than that observed for the materials
micrographs of the Nb2O5–K2CO3 (Fig. 4-A) show that the material is synthesized using C4H4NNbO9⋅xH2O; this is likely due to the presence of
composed of large particles over which smaller nodular particles are non-stoichiometric niobates and residual Nb2O5, as the presence of
deposited. Regarding the Nb2O5–KOH, the morphology of the material dopant structures may lead to the distortion of Nb–O–Nb symmetric
shows a transition between large particles and the cuboid-like structure stretching modes, giving rise to the band softening observed [43].
that is typically characteristic of potassium niobate. Both these patterns Furthermore, reports in the literature show that the B1(TO2) mode is
of behavior are consistent with the notion that the diffusion of K2O related to the appearance of the spontaneous polarization property of
through Nb2O5 particles limited the efficient formation of KNbO3 in this ferroelectric KNbO3 [24]. Thus, it seems that all the materials synthe­
synthesis pathway, as this duality in morphological characteristics may sized in this study, with the exception of Nb2O5–KNO3, exhibit ferro­
very well represent the phase transition process that occurred during the electric properties. The suppression of the B1(TO2) mode in

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Fig. 3. Scanning electron micrographs (25000x, 50000x, and 250000x) of the materials synthesized using C4H4NNbO9⋅xH2O as niobium source: A) NbOxa-K2CO3; B)
NbOxa-KNO3; C) NbOxa-KOH; and D) NbOxa-C8H5KO4.

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Fig. 4. Scanning electron micrographs (25000x, 50000x, and 250000x) of the materials synthesized using Nb2O5 as niobium source: A) Nb2O5–K2CO3; B)
Nb2O5–KNO3; C) Nb2O5–KOH and; D) Nb2O5–C8H5KO4.

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Table 2 [34,44].
Specific surface areas of the materials synthesized in this study estimated Fig. 6 shows the diffuse reflectance absorption spectra of the mate­
through the application of the BET method. rials, along with a visual illustration of the powders obtained.
Material Specific surface area Material Specific surface area As can be observed in Fig. 6, the optical properties of the materials
(m2g− 1) (m2g− 1) vary significantly according to the potassium precursor used during the
NbOxa- 3.20 Nb2O5–K2CO3 7.36 synthesis process. The visual illustration of the powders obtained shows
K2CO3 that some materials exhibit blue coloration; this is particularly observed
NbOxa-KNO3 0.13 Nb2O5–KNO3 2.12 for the NbOxa-KOH and Nb2O5–C8H5KO4 samples. This behavior, when
NbOxa-KOH 9.47 Nb2O5–KOH 6.68
analyzed through the absorption spectrum of the materials, can be
NbOxa- 5.85 Nb2O5–C8H5KO4 6.69
C8H5KO4 correlated to an extension in visible light absorption of NbOxa-KOH and
Nb2O5–C8H5KO4. According to the related literature, the occurrence of
bluish coloration in KNbO3 is intrinsically linked to the presence of
Nb2O5–KNO3 may be attributed to the presence of the niobium-rich oxygen surface defects, which are able to create intermediate band
K2Nb4O21 phase, which is not likely to possess a ferroelectric nature. states, leading to the enhancement of the light absorption capacity of the
Finally, the Raman spectrum of Nb2O5–KOH is also found to display a semiconductor [45]. In addition, as observed in the scanning electron
large band located at approximately 700 cm− 1; this can be associated micrographs of the NbOxa-KOH and Nb2O5–C8H5KO4 samples (Fig. 3C
with the stretching mode of the Nb–O–Nb linkage present in the residual and 4D), both of these materials are characterized by cuboid-like
Nb2O5, which has a mass fraction of approximately 9% in the sample structures with sharp edges, which are reportedly defect-rich regions

Fig. 5. Raman spectra of the synthesized potassium niobates.

Fig. 6. A) Absorption spectrum and illustration of the materials synthesized using C4H4NNbO9⋅xH2O as niobium source; B) Absorption spectrum and illustration of
the materials synthesized using Nb2O5 as niobium source.

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in niobium-based structures; this observation corroborates the idea that process [53]. Finally, the 2p spectrum of potassium is shown in Fig. 7C.
the presence of oxygen defects led to the optical modifications observed The spectrum was deconvoluted into two main peaks, which can be
in the materials [46,47]. related to the 2p1/2 and 2p3/2 modes of the K+ cation [54].
The bandgap energy of the niobates synthesized in this study was
estimated using the direct method proposed by Ghobadi et al. (see
Equation (1) below) [48,49]. 3.2. Photocatalytic analysis of NbOxa-P
( )1/m ( )
Abs 1 1 In order to choose the most suitable pure KNbO3 sample for appli­
= C1 − + C2 (1)
λ λ λgap cation in the hybrid piezophotocatalytic ozonation process, the photo­
catalytic activity of the NbOxa-P samples was evaluated through the
Where Abs represents the absorption associated with a specific wave­ discoloration of methylene blue under ultraviolet irradiation. The re­
length (λ), C1 and C2 are empirical constants, λgap is the wavelength sults obtained from this analysis are shown in Fig. 8A. Fig. 8B shows the
associated with the prohibited band, and m is a factor that can take on linear fitting of the photocatalytic data to a pseudo-first-order kinetic
different values depending on the type of transition considered. Here, model (Equation (3)), which is commonly used to describe photo­
the value of m must be equal to 0.5, as it is related to direct transitions. catalytic reactions [55]:
The 1/λgap parameter required to calculate the bandgap energy can
( )1/0.5 C
be extracted by the extrapolation of the linear section of the Abs ln = − kp t (3)
λ C0
plot to y = 0. The bandgap energy can then be calculated using Equation
(2) below [48]: where C represents the concentration of methylene blue at any given
time t, C0 is equal to the concentration of methylene blue after the
1240
Egap = (2) adsorption equilibrium, and kp is the apparent photocatalytic reaction
λgap
rate constant.
where Egap is the bandgap energy of the semiconductor (eV). First, it is worth pointing out that all the NbOxa-P samples exhibited
Table 3 shows the bandgap energies obtained for the materials syn­ a similar MB adsorption capacity – of about 3 mg g− 1. The photocatalytic
thesized in this work. evaluation of NbOxa-P showed that the material produced using po­
Unsurprisingly, both the NbOxa-KOH and Nb2O5–C8H5KO4 samples tassium hydrogen phthalate as a precursor (NbOxa-C8H5KO4) exhibited
recorded relatively lower bandgap energy values compared to all the the highest efficiency in terms of methylene blue discoloration; this
materials synthesized in this study, as related to their larger visible light material recorded approximately 70% MB discoloration after being
absorption capacity derived from the probable existence of oxygen de­ subject to ultraviolet irradiation for 1 h. The second best material was
fects. Furthermore, the materials synthesized using C4H4NNbO9⋅xH2O as NbOxa-KOH, which recorded approximately 45% discoloration after 1
the niobium source generally recorded lower bandgap energies h. These results may be attributed to the specific surface area and
compared to the Nb2O5-based materials; this behavior is likely attrib­ morphology of these materials. NbOxa-C8H5KO4 exhibited the highest
uted to the presence of residual amounts of niobium oxide, as this oxide specific surface area among the materials with smooth cubic particles,
has a slightly larger bandgap energy (3.4 eV) when compared to KNbO3 and this probably enlarged the interface available to carry out the su­
(3.2 eV) [9]. perficial processes involved in the photocatalytic mechanism. On the
Aiming to further verify the existence of oxygen defects on the sur­ other hand, although NbOxa-KOH exhibited the highest specific surface
face of the blue-tinted niobates, the XPS spectra of the NbOxa-KOH (blue area among the NbOxa-P samples, the existence of surface defects on the
color) and NbOxa-C8H5KO4 (white color) were measured. Fig. 7 shows sharp edges of its particles may have led to the increased recombination
the results obtained. of the photogenerated charges; according to reports in the literature,
Observing Fig. 7A, it was possible to deconvolute three peaks from excessive quantities of oxygen vacancies may act as recombination
the obtained O 1s spectrum. The first one (OL, ≈529.3 eV) is related to centers during the photonic activation process [56,57]. Thus, this
the superficial lattice oxygen of the KNbO3 structure, whereas the sec­ increased recombination may have counterbalanced the beneficial effect
ond (OV, ≈531eV) and third peaks (OA, ≈532.5eV) can be related to of the higher specific surface area, hindering the efficiency of
oxygen vacancies in the matrix of the niobates and hydroxyl (O–H) NbOxa-KOH in terms of the photodiscoloration of methylene blue.
groups, respectively [50,51]. It is noticeable that the peak related to the Fig. 8B shows that the proposed kinetic model can be safely used to
presence of oxygen vacancies is much more prominent in the describe the photocatalytic process, as the values obtained for R2 are
NbOxa-KOH spectrum, agreeing with the assumption that these species fairly close to 1. Furthermore, the NbOxa-C8H5KO4 sample was found to
were responsible for the blue tint observed in such niobate. exhibit the best photocatalytic efficiency in terms of methylene blue
The Nb 3d spectrum (Fig. 7B) was deconvoluted into 4 main peaks. discoloration, as this niobate recorded the highest kp value among the
The two peaks with higher intensities, located at 207 eV and 210 eV, can materials tested; to be precise, its kp value was almost twice the value
be related to the 3d5/2 and 3d3/2 modes of the Nb+5, respectively, which obtained for the NbOxa-KOH photocatalyst. Thus, the NbOxa-C8H5KO4
are characteristic of the potassium niobate [52]. On the other hand, the material was selected for application in the piezophotocatalytic ozona­
peaks with lesser intensity are linked to the presence of Nb+4 on the tion process.
surface of the niobates; this behavior was probably derived from the Fig. 9 shows the chronoamperometry and open-circuit potential
existence of the oxygen vacancies observed in Fig. 7A, similar to the (OCP) tests performed for the NbOxa-P, aiming to further evaluate their
results described by Li et al. (2016) in the niobium oxide pyrolysis photocatalytic properties.
Fig. 9A shows that the NbOxa-C8H5KO4 achieved the highest
photocurrent generation in the chronoamperometry tests, as expected
Table 3 due to its superior photoactivity for the MB discoloration. Therefore, it is
Bandgap energies obtained for the materials synthesized in this study based on expected that the mobility of photogenerated charges during the pho­
the application of the Ghobadi method.
tonic activation of the NbOxa-C8H5KO4 is superior to the ones achieved
Material Gap energy (eV) Material Gap energy (eV) by the other potassium niobates. Furthermore, the photocurrent gener­
NbOxa-K2CO3 3.26 Nb2O5–K2CO3 3.29 ation for the other NbOxa-P followed the same behavior observed in the
NbOxa-KNO3 3.25 Nb2O5–KNO3 3.35 photocatalytic tests, corroborating the results obtained in Fig. 8.
NbOxa-KOH 3.20 Nb2O5–KOH 3.39 As for the OCP tests (Fig. 9B), it is possible to establish a correlation
NbOxa-C8H5KO4 3.29 Nb2O5–C8H5KO4 3.26
between the surface recombination of photogenerated charge carriers

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Fig. 7. XPS spectrum of the NbOxa-KOH and NbOxa-C8H5KO4: A) O1s; B) Nb 3d; C) K 2p.

Fig. 8. A) Photocatalytic discoloration of methylene blue using NbOxa-P potassium niobates as photocatalysts; B) Linear fitting of the photocatalytic data to the
pseudo-first-order model. (For interpretation of the references to color in this figure legend, the reader is referred to the Web version of this article.)

Fig. 9. A) Chronoamperometry results for the NbOxa-P; B) OCP results for the NbOxa-P.

and the variation in open-circuit potential (dOCP/dt) when the light ( )− 1

irradiation is switched off, as a faster recombination process can be τn =
kb T dOCP
(4)
inferred from higher values of dOCP/dt. Equation (4) can be employed to e dt
estimate the average lifetime of photogenerated charge carriers by uti­
lizing the data obtained from the OCP experiments [58].: where τn is the average lifetime of photogenerated charge carriers (s), kb
is equal to the Boltzmann constant (1.38 × 10–23 J K− 1), T is the tem­
perature of system (K), e is the elementary charge of a single electron
(1.602 × 10− 19 C), and dOCP/dt is the voltage change slope at the

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moment irradiation was turned off. and photo-ultrasonication hybrid processes, the synergy between the
Table 4 shows the results obtained through the application of individual processes contributed to the enhancement of MB discolor­
Equation (4). ation. Furthermore, in the case of the photo-ozonation process, the
Table 4 shows that the NbOxa-KOH achieved the lowest average incidence of ultraviolet radiation probably led to the photolysis of the
lifetime of photogenerated charge carriers among the NbOxa-P. This ozone molecule into hydroxyl active radicals, as expressed in Equations
finding is consistent with the theory that the presence of surface defects (7) and (8) below [64]:
on the sharp edges of its particles may have contributed to the accel­ ( )
(7)
λ>310nm
erated recombination of photogenerated charges. Additionally, the O3 ̅̅̅̅̅̅→ O 1 D + O2
other NbOxa-P presented similar behaviors, with the NbOxa-C8H5KO4 ( )
achieving the highest τn value (6.6 s) and further confirming its position O 1 D + H2 O →2• OH (8)
as the superior potassium niobate photocatalyst.
Finally, the photo-ozonation-ultrasonication process was able to
successfully merge the effects of the three individual processes into an
3.3. Evaluation of the piezophotocatalytic ozonation process efficient hybrid process, resulting in a higher discoloration of the MB
molecule. This outcome may be attributed to the enhanced formation of
Fig. 10 shows the results obtained from the methylene blue discol­ hydroxyl radicals due to the parallel effect of the reactions described in
oration analysis performed using a wide range of advanced oxidation Equations (5)–(8), along with the direct oxidation promoted by the
processes, divided into two groups: in the presence and absence of the ozone molecule.
NbOxa-C8H5KO4 potassium niobate (employed as a heterogeneous Regarding the tests involving the application of the NbOxa-C8H5KO4
catalyst). Fig. 10A shows the results obtained for direct photolysis, as the heterogeneous catalyst, Fig. 10B shows that the presence of the
ozonation, ultrasonication, photo-ozonation, photo-ultrasonication, KNbO3 resulted in significant improvements in MB discoloration for all
ozonation-ultrasonication, and photo-ozonation-ultrasonication pro­ processes evaluated. First, the heterogeneous photocatalysis process
cesses, while Fig. 10B shows the results obtained for heterogeneous exhibited superior performance over the photolysis process mainly due
photocatalysis, catalytic ozonation, piezocatalysis, photocatalytic to the formation of hydroxyl and superoxide radicals by the photo­
ozonation, piezophotocatalysis, piezocatalytic ozonation, and piezo­ generated charge carriers located at the conduction and valence bands
photocatalytic ozonation. Finally, Fig. 10C and D shows the absorption (CB and VB, respectively) of the potassium niobate, as described in
spectra of the aliquots collected during the photo-ozonation- Equations (9)–(11) below [65]:
ultrasonication and piezophotocatalytic ozonation of methylene blue,
respectively. hv
KNbO3 →e− (CB) + h+ (VB) (9)
Looking at Fig. 10A, one will first notice that both the photolysis and
ultrasonication processes were unable to significantly promote the •
H2 O + h+ (VB) → OH + H + (10)
discoloration of MB present in the system; the processes recorded a
maximum discoloration of about 10% after 1 h of treatment. The O2 + e− (CB)→O•−2 (11)
mechanism involving the ultrasonication process is largely based on the
The results obtained from the piezocatalysis test involving the use of
formation of hydroxyl radicals through the decomposition of water
the NbOxa-C8H5KO4 confirm the piezoelectric nature of potassium
molecules via ultrasonic cavitation (UC) (Equation (5)), while the
niobate and its ability to promote the generation of active radicals
discoloration of MB solely under UV light is based on the photosensiti­
through the polarization field created by ultrasonic vibration, which led
zation of the dye molecule, where electrons are excited via UV radiation,
to the enhancement of MB discoloration when compared to the ultra­
promoting the homolytic cleavage of chemical bonds and the generation
sonication process. The catalytic ozonation process also exhibited su­
of active radicals in the presence of dissolved oxygen (Equation (6))
perior performance over the simple ozonation process in terms of MB
[59–61].
discoloration; as reported in the literature, the ozone molecule is able to
UC •
H2 O ̅→ OH + H + (5) react with functional groups (such as Lewis acid sites) and oxygen va­
cancies located on the surface of KNbO3 in order to generate active
radicals such as O•−2 , • OH and • O [66].
(6)
UV
MB̅→ MB∗ + O2 → MB+∗ + O•−2
The photocatalytic ozonation and piezocatalytic ozonation processes
Continuing the analysis of Fig. 10A, the ozonation process exhibited exhibited superior performance over the photocatalysis, piezocatalysis,
an intermediate ability to promote the discoloration of MB, mainly due and catalytic ozonation processes due to the combination of the active
to the direct oxidation reaction between the dye and the ozone molecule. radical generation mechanisms discussed in the previous paragraphs.
However, this process is reported to be incapable of completely miner­ Furthermore, regarding the photocatalytic ozonation process, it should
alizing organic compounds in aqueous media due to the formation of be noted that the adsorbed ozone molecules can react with both pho­
stable intermediates, such as saturated carboxylic acids and inactivated togenerated electrons and superoxide radicals in order to promote the
aromatics, which explains the slow discoloration rate observed at the formation of the O•−
3 radical, which is subsequently transformed into the
end of the process [12,62]. The ozonation-ultrasonication process •
OH radical, as can be observed in the reactions presented in Equations
exhibited virtually the same results as the ozonation process; this shows (12)–(15) below [12,14]:
that the addition of ultrasonication may have contributed toward the
O3 + e− (CB)→O•−3 (12)
decomposition of some of the ozone species into non-reactive species, as
previously reported in the literature [63]. As for the photo-ozonation
O3 + O•−2 → O•−3 + O2 (13)

Table 4 O•−3 + H + →HO•3 (14)

Average lifetime of photogenerated charge car­
riers (τn) calculated from the OCP tests. HO•3 → • OH + O2 (15)
Material τn (s)
NbOxa-K2CO3 5.6
In the case of the piezophotocatalysis process, the enhanced efficiency
NbOxa-KNO3 5.2 observed in MB discoloration can be credited to the enhanced separation
NbOxa-KOH 2.6 of photogenerated charges propelled by the intrinsic magnetic field
NbOxa-C8H5KO4 6.6 generated in the piezoelectric KNbO3, which facilitated the mechanisms

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Fig. 10. A) AOPs tested in the absence of KNbO3 as catalyst; B) AOPs tested in the presence of KNbO3 as catalyst; C) Absorption spectra of the aliquots collected
during the photo-ozonation-ultrasonication of MB; D) Absorption spectra of the aliquots collected during the piezophotocatalytic ozonation of MB.

involving the generation of active radicals [67]. catalyst, the process is unable to promote the proper degradation of MB
Finally, the newly proposed piezophotocatalytic ozonation process [55].
exhibited the best efficiency in MB discoloration among all the processes Fig. 11 shows the results obtained from the scavenger tests per­
investigated; this can be attributed to the synergy between all the formed for the piezophotocatalytic ozonation process, aiming to eval­
mechanisms involving the generation of active radicals proposed in the uate the role played by active radicals in the discoloration of the MB
previous paragraphs. The hybrid process was the only process that was molecule.
capable of promoting the complete discoloration of MB in 1 h; clearly, The results obtained from the scavenger tests show that both hy­
this points to its great potential for application toward the treatment of droxyl and superoxide active radicals play a significant role in the
industrial wastewater. A comparison of Fig. 10C and D shows that the discoloration of the MB molecule. The suppression of hydroxyl radical
application of potassium niobate as a catalyst played an important role
in the discoloration of MB since the characteristic peaks of the dye can
still be observed in the photo-ozonation-ultrasonication spectra. During
the discoloration process, the disappearance of the peak centered at 673
nm is associated with the removal of the chromophoric group of MB on
the central aromatic heterocycle (N–S conjugated structure). In this
context, one notices that this peak remained centered at 673 nm during
the piezophotocatalytic ozonation process; essentially, this shows that
no other chromophore molecules were created as byproducts – these
byproducts include Azure A (C14H14ClN3S, λmax = 620 nm), Azure B
(C15H16ClN3S, λmax = 650 nm), Azure C (C13H12N3S+, λmax = 610 nm),
and thionine blue (C12H9N3S ⋅ C2H4O, λmax = 600 nm) [68]. Further­
more, the peaks located at 292 nm and 245 nm are found to correspond
to heteropolyaromatic bonds and benzene rings of the MB molecule, and
their disappearance without the formation of new absorption peaks is
associated with the degradation of the MB molecule into smaller
aliphatic intermediates with lower molecular weight [68]. Finally, the
absorption spectra of the aliquots collected during the
photo-ozonation-ultrasonication process (Fig. 10C) show that the band
located between 305 and 325 nm was not reduced in a significant
manner during the process; this can be attributed to the accumulation of
leucomethylene blue (C16H19N3S, λmax = 250 and 310 nm) intermediate,
which essentially implies that, in the absence of the potassium niobate Fig. 11. Analysis of active radical suppression in the piezophotocatalytic
ozonation process.

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led to a 60% reduction in the discoloration of MB, whereas the sup­ Table 5
pression of superoxide radical resulted in 35% loss of efficiency. Thus, it Kinetic data obtained for the methylene blue discoloration tests conducted in
is evident that the formation of both active radicals is necessary to this study.
achieve the high efficiency observed for the piezophotocatalytic ozon­ Process kapp(min− 1) R2
ation process. The hydroxyl radical is widely known as the major active Photolysis 0.0016 0.987
radical involved in AOPs applied for the degradation of MB, while su­ Ozonation 0.0160 0.931
peroxide radical is found to either react directly with MB or promote the Ultrasonication 0.0015 0.996
formation of more hydroxyl active radicals, as shown in Equations (16) Photo-ultrasonication 0.0087 0.988
Photo-ozonation 0.0220 0.980
and (17) below [69,70]:
Ozonation-ultrasonication 0.0016 0.966
•
OH + • OH →H2 O2 (16) Photo-ozonation-ultrasonication 0.0277 0.989
Photocatalysis 0.0197 0.988
Catalytic ozonation 0.0232 0.977
H2 O2 + O•−2 → • OH + O2 + OH − (17) Piezocatalysis 0.0053 0.989
Photocatalytic ozonation 0.0352 0.967
Fig. 12 shows a schematic representation of the mechanisms
Piezophotocatalysis 0.0327 0.996
involving the generation of active radicals under the hybrid piezopho­ Piezocatalytic ozonation 0.0274 0.976
tocatalytic ozonation process. Piezophotocatalytic ozonation 0.0621 0.997
For the kinetic analysis of the processes investigated, the same
pseudo-first-order model employed previously (Equation (3)) was used;
it should be noted however that the reaction rate constant was renamed the synthesis performed using powdered niobium oxide as the niobium
to kapp, which indicates an apparent reaction rate constant. The results source. The formation of pure KNbO3 is probably associated with a
obtained are shown in Table 5. higher chemical homogeneity derived from the application of water-
Once again, the kinetic parameters obtained show that all the pro­ soluble precursors. In optical terms, the potassium niobates exhibited
cesses are in good agreement with the model proposed in this study, with different properties according to the potassium precursor employed in
the exception of the individual and binary ozone-based processes (these the synthesis, and these differences were reflected in the morphology of
processes recorded lower R2 values). These processes were probably each of the materials. NbOxa-C8H5KO4 exhibited the best photocatalytic
inconsistent with the proposed model due to the deceleration of MB activity among the NbOxa-P samples investigated; this outcome was
discoloration observed at the final stages of the tests; this behavior is mainly due to the morphological and electrical characteristics of the
linked to the lower capacity of ozone to degrade the reaction in­ material – including specific surface area, particle shape, and charge
termediates - including the molecules Azure A, Azure B, and Azure C, all recombination. The hybrid piezophotocatalytic ozonation process using
of which present a maximum absorption close to that of methylene blue the NbOxa-C8H5KO4 as catalyst exhibited the highest efficiency in terms
[55]. Interestingly, the ternary photo-ozonation-ultrasonication and of MB discoloration among all the processes evaluated, being the only
piezophotocatalytic ozonation processes were found to be in line with process that promoted 100% MB discoloration after 1 h of treatment. For
the proposed model; this shows that the synergy between the three the advanced oxidation processes evaluated, the degree of efficiency in
processes helped to circumvent the shortcomings/constraints presented terms of MB discoloration reflected the following order: Ultrasonication
by the ozone-based degradation routes. Finally, the piezophotocatalytic < Photolysis < Piezocatalysis < Photo-ultrasonication < Ozonation <
ozonation process recorded the highest kapp value for the MB discolor­ Ozonation-ultrasonication < Photocatalysis < Catalytic ozonation <
ation, further confirming its position as the most efficient process among Photo-ozonation < Piezocatalytic ozonation < Photo-ozonation-ultra­
the AOPs evaluated in this work. sonication < Photocatalytic ozonation < Piezophotocatalysis < Piezo­
photocatalytic ozonation. Thus, based on the results obtained, one can
confirm that the synergy between the combined AOPs contributed
4. Conclusion
significantly toward enhancing the efficiency of the proposed hybrid
process, highlighting its potential use for the remediation of aqueous
Based on the findings of the present study, one can conclude that the
effluents.
application of ammonium niobate (V) oxalate hydrate
(C4H4NNbO9⋅xH2O) as the niobium source in the proposed synthesis
pathway resulted in the efficient formation of the desired potassium Declaration of competing interest
niobate (KNbO3) in the orthorhombic form, without the formation of
non-stoichiometric niobates or residual niobium oxide, as observed in The authors declare that they have no known competing financial

Fig. 12. Mechanisms involving the generation of active radicals proposed under the piezophotocatalytic ozonation process.

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interests or personal relationships that could have appeared to influence through reactor, J. Hazard Mater. 405 (2021), https://doi.org/10.1016/j.
jhazmat.2020.124277.
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FAPESP (Grants #2014/50945-4, #2017/10118-0, and #2022/04058- (2021) 3–10, https://doi.org/10.1016/j.jallcom.2021.160641.
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