Structural and Photocatalytic Studies on Oxygen Hyperstoichiometric Titanium-Substituted Strontium Ferrite Nanoparticles

Abstract

Doping of ferrites is an important domain of research for their application as photocatalysts. In the present work, the effect of Ti⁴⁺ substitution on the structural and photocatalytic properties of strontium ferrite nanoparticles (NPs) is studied. Ternary doped Sr_1−xTi_xFe₂O_4+δ ferrite NPs (x = 0.0–1.0) were synthesized by sol–gel methodology. Tetravalent Ti⁴⁺ ions caused oxygen hyperstoichiometry and enhancement in the surface area from 44.3 m²/g for SrFe₂O₄ NPs to 77.6 m²/g for Sr_0.4Ti_0.6Fe₂O_4+δ NPs. The average diameter of NPs ranged between 25–35 nm as revealed by TEM analysis. The presence of two sextets in the Mössbauer spectrum of pristine SrFe₂O₄ and Ti⁴⁺-substituted ferrite NPs and a paramagnetic doublet in the TiFe₂O₅ confirmed their phase purity. The photocatalytic potential of pure and Ti⁴⁺-substituted ferrite NPs was studied using nitroaromatic compounds, viz. pendimethalin, p-nitrophenol and Martius yellow, as model pollutants. Doped ferrite NPs with a composition of Sr_0.4Ti_0.6Fe₂O_4+δ NPs showed the highest degradation efficiency ranging from 87.2% to 94.4%. The increased photocatalytic potential was ascribed to the lowering of band gap (E_g) from 2.45 eV to 2.18 eV, a fourfold decrease in photoluminescence intensity, increased charge carrier concentration (4.90 × 10¹⁵ cm⁻³ to 6.96 × 10¹⁵ cm⁻³), and decreased barrier height from 1.20 to 1.02 eV. O₂^●− radicals appeared to be the main reactive oxygen species involved in photodegradation. The apparent rate constant values using the Langmuir–Hinshelwood kinetic model were 1.9 × 10⁻² min⁻¹, 2.3 × 10⁻² min⁻¹ and 1.3 × 10⁻² min⁻¹ for p-nitrophenol, pendimethalin and Martius yellow, respectively. Thus, tuning the Ti⁴⁺ content in strontium ferrite NPs proved to be an effective strategy in improving their photocatalytic potential for the degradation of nitroaromatic pollutants.

1. Introduction

Water contamination caused by industrialization and urbanization is a global concern. Organic pollutants such as pharmaceuticals, dyes and pesticides have detrimental effects on the ecosystem [1,2,3,4]. This drives research toward the remediation of these hazardous organic pollutants [5,6]. Different approaches have been employed for their removal including electrocatalysis, photocatalysis, reverse osmosis, adsorption, biological treatment and chemical precipitation [7,8]. Photocatalysis is regarded as the most effective approach among other methods because of various advantages such as energy conservation, high efficiency and production of environmentally benign end products [9]. It is accompanied by the generation of active oxygen species over the photocatalyst’s surface using visible or ultraviolet light. Commonly used auspicious photocatalysts, viz. ZnO and TiO₂, are less active in visible light because of wide band gap energy of 3.0 eV and can be effective only under UV light [10]. However, sunlight comprises only 3–4% of UV light, highlighting the significance of visible-light-driven photocatalysts. Spinel ferrites have comparatively narrow band gap values (2.0 eV), which ensures the high absorption of visible light, which constitutes 46% of solar light [11,12]. This feature coupled with the long lifetime of photo-induced electron-hole pairs have made them extensively studied materials for photodegradation of organic pollutants [13,14,15,16,17]. They have the general formula AB₂O₄, where A and B refers to tetrahedrally (T_d) and octahedrally (O_h) coordinated lattice sites, respectively, which can be accommodated by different ions with a ferric ion (Fe³⁺) as the primary component [18,19,20,21]. The diverse combination of elements in the form of bi- and tri-metallic spinel ferrite nanostructures imparts novel magnetic and structural features, which makes them attractive candidates for varied applications [22,23].

Apart from bi-metallic spinel ferrites, different tri-metallic ferrite NPs can also be synthesized with an appropriate mixture of metal ions. They have enhanced photocatalytic potential compared to bimetallic ferrites [24]. The presence of dopant elements favors larger heterogeneous surface area and provides more surface-active sites [25,26]. Lanthanum doped barium ferrite with a 2% molar ratio of dopant ion has been reported as an active photocatalyst for the mineralization of methylene blue (MB) dye when exposed to ultraviolet and visible light. [25]. The enhanced photodegradation potential of Mg_0.6Zn_0.2Fe₂O₄ NPs under ultraviolet light has been reported for the photodegradation of MB dye, rather than undoped ferrite NPs [26].

The existence of an excess of oxide ions in spinel ferrite NPs causes oxygen hyperstoichiometry. It accelerates the electrochemical and photocatalytic reactions [27,28,29]. Oxygen hyperstoichiometric tri-metallic Zn_1−xMn_xAl₂O_4+δ spinels (0 < x < 1) were synthesized for reducing nitrobenzene to nitrosobenzene [30]. The Mn³⁺ ions served as active sites for reducing nitrobenzene and doping resulted in the generation of cationic vacancies. Oxygen hyperstoichiometric Mg_0.5Ti_0.5Fe₂O_4.5 nanoparticles (NPs) have been reported to exhibit 98% photodegradation for rhodamine B dye [31]. Among different ferrites, strontium ferrites (SrFe₂O₄) have advantages of mesoporous morphology, large surface area along with the potential for the occurrence of oxygen vacancies due to large size of Sr²⁺ ions [13,14,15]. They have been reported for the effective remediation of dyes and selective oxidation of styrene [15,16,17]. The excellent magnetic properties of SrFe₂O₄ NPs further assist in their recovery after water treatment [13]. Ti⁴⁺-substituted strontium ferrite NPs have not been studied for their magnetic, structural and photocatalytic features. In the present work, the effect of Ti⁴⁺ substitution on the magnetic, structural, optical and photocatalytic properties of oxygen hyperstoichiometric Sr_1−xTi_xFe₂O_4+δ (x = 0.0, 0.3, 0.6 & 1.0) NPs was studied. The Ti⁴⁺ content was optimized for the application of Ti⁴⁺-substituted ferrite as a photocatalyst under ultraviolet and visible light illumination. The maximum photodegradation potential was achieved for the NPs with the formula Sr_0.4Ti_0.6Fe₂O_4.6. The greater oxygen hyperstoichiometry, specific surface area and lower band gap have made Sr_0.4Ti_0.6Fe₂O_4.6 NPs superior to pristine NPs. The visible-light-assisted degradation of nitroaromatic pollutants, viz. p-nitrophenol, pendimethalin and Martius yellow, was examined in detail. The United States Environmental Protection Agency (USEPA) has classified these nitroaromatic compounds as ‘persistent-bioaccumulative toxins’ [32,33,34]. The substitution of tetravalent Ti⁴⁺ ions in SrFe₂O₄ NPs resulted in oxygen hyperstoichiometry, increased surface area and surface heterogeneity, which are ideal attributes for enhancing photocatalytic efficiency. It also improved the charge transfer and light absorption, which further assisted in the photocatalytic activity. The capacitance studies were also performed to determine the charge-carrier concentration and barrier height. The impact of various reaction parameters, viz. solution pH (1.0–9.0), contact time (2 min–720 min) and catalyst dose (0.01 g/L–1.0 g/L), on the photodegradation was also ascertained. The Langmuir–Hinshelwood kinetic model was employed for the evaluation of the apparent rate constant. The plausible photodegradation mechanism was proposed on the basis of quenching experiments, band gap studies and GC-MS analysis.

2. Materials and Methods

2.1. Chemicals and Characterization

The chemicals used, viz. strontium nitrate (Sr(NO₃)₂·6H₂O), tetrabutyl titanate ((CH₃(CH₂)₃O)₄Ti), citric acid (C₆H₈O₇), ammonium hydroxide (NH₄OH) (30%), ferric nitrate ((Fe(NO₃)₃·9H₂O), hydrogen peroxide (H₂O₂), Martius yellow (C₁₀H₆N₂O₅), p-nitrophenol (C₆H₅NO₃) and pendimethalin (C₁₃H₁₉N₃O₄), were of AR grade. In deionized water, the working solutions of various concentrations were prepared. The phase constitutes and the crystalline nature was examined employing X-ray diffraction (XRD) analysis. Fourier transform–infrared spectroscopy (FT-IR) measurements were conducted to detect the presence of functional groups. Morphological studies of the synthesized nanocatalysts were conducted by scanning electron microscopy–energy dispersive X-ray spectroscopy (SEM-EDS) and transmission electron microscopy (TEM) analyses. The specific surface areas were evaluated from nitrogen adsorption–desorption Brunauer–Emmett–Teller (BET) experiments. A vibrating sample magnetometer (VSM) and Mössbauer spectroscopy were used to examine the magnetic properties. Capacitance–voltage measurements were performed to evaluate the barrier height and carrier concentration. The instrumental details are given in Text S1. The iodometric titration method was employed to evaluate the oxygen content of the synthesized ferrite NPs [35] and the details are given in Text S2. Zeta potential measurements (explained in Supplementary Material Text S3) were used to evaluate the surface charge of the synthesized NPs.

2.2. Synthesis of Pure and Ti⁴⁺ Substituted Ferrite NPs

The pure and Ti⁴⁺-substituted strontium ferrite NPs with different compositions, viz. Sr_1−xTi_xFe₂O_4+δ (x = 0.0, 0.3, 0.6 and 1.0), were synthesized employing the sol–gel auto-combustion approach. The pristine bi-metallic ferrite NPs were synthesized by mixing the Sr(NO₃)₂·6H₂O/(CH₃(CH₂)₃O)₄Ti salts with (Fe(NO₃)₃·9H₂O in a 1:2 molar ratio in 20 mL of distilled water. Citric acid (C₆H₈O₇), as chelant in a molar ratio of 1:1 with respect to metal salts, was added, followed by the dropwise addition of NH₄OH (25%) to adjust the pH = 8.0. The resulting mixture was magnetically agitated at temperature of 80 °C until it was transformed into sol. The stirring was continued at 150 rpm for 10 min, which led to the conversion of sol into xerogel. It was oven dried at 100 °C for 24 h and crushed into a fine powder. The obtained nanopowders were calcined at 300 °C for 3 h to get ferrite powders as the final thermolysis product. The same procedure was followed for the synthesis of tri-metallic ferrite NPs with the different stoichiometric ratios of precursor materials Fe(NO₃)₃·9H₂O, Sr(NO₃)₂·6H₂O and (CH₃(CH₂)₃O)₄Ti). The flow chart depicting the synthesis procedure of Sr_1−xTi_xFe₂O_4+δ NPs (x = 0.0–1.0) is given in Scheme S1.

2.3. Photocatalytic Studies

The photocatalytic activity of pristine and Ti⁴⁺-substituted ferrite NPs was examined for the degradation of three nitroaromatic compounds using a mercury lamp, 125 W power, and a light-emitting diode, 60 W power, as the sources of UV and visible light, respectively. Standard stock solutions of p-nitrophenol and Martius yellow were prepared in deionized water, whereas for the pendimethalin mixture of methanol, water was used as a solvent (2:3, v/v). By adding deionized water to the stock solutions, working solutions with various initial concentrations were prepared. The first experiment was conducted to ascertain the best photocatalyst with a 0.1 g/L dose of the NPs dispersed in 100 mL of p-nitrophenol (0.5 mg/L), pendimethalin (0.5 mg/L) and Martius yellow (0.05 mg/L). The best photocatalyst screened from the preliminary studies was then used for the detailed analysis. The impact of the solution’s pH was estimated by varying the pH using NaOH (0.1 M) and HCl (0.1 M). The dose of NPs was varied from 0.01 g/L to 1.0 g/L at optimum pH. The suspensions were shaken in an orbital shaker at 120 rpm for 30 min with the addition of H₂O₂ (0.5 mL) before the irradiation of light for establishing adsorption–desorption equilibrium. The aliquot (1 mL) of the dispersion was taken out after regular time intervals followed by centrifugation. The supernatant solutions were then examined for changes in concentration using UV–visible spectrophotometry. The λ_max for p-nitrophenol, pendimethalin and Martius yellow was 398, 465 and 445 nm, respectively. The degradation (%) of nitroaromatic pollutants (Equation (1)) and the kinetic studies were conducted according to the Langmuir–Hinshelwood kinetics (Equation (2)) as given below:

(1)$\mathrm{Degradation} (\%)=\frac{{\mathrm{C}}_{\mathrm{i}}{-\mathrm{C}}_{\mathrm{t}}}{{\mathrm{C}}_{\mathrm{t}}}\times 100\%$

(2)$\ln \left({\mathrm{C}}_{\mathrm{t}}/ \mathrm{C}\right)=\mathrm{kt}$

where C and C_t stand for the concentration of nitroaromatic contaminant after the establishment of adsorption–desorption equilibrium and the concentration left after a fixed time period (t) of illumination, respectively, and k is the apparent rate constant. Limits of quantification (LOQ) and limits of detection (LOD) were also determined for p-nitrophenol, pendimethalin and Martius yellow as given in Supplementary Text S4. The photocatalyst (0.01 g) was sonicated for two hours in 5 mL of dimethyl sulfoxide to detect photoluminescence. Then, fluorescence experiments were performed on the diluted solution (in a 1:1 ratio) to record the emission spectra in the wavelength ranging from 200 nm to 800 nm.

The effect of quenching agents on the photodegradation of nitroaromatic pollutants was also evaluated; 1 mL of 10 mM aqueous solution of ethylene diamine tetraacetate (EDTA, h⁺ scavenger), methanol (C₂H₅OH, •OH scavenger), ascorbic acid (C₆H₈O₆, •O₂⁻ scavenger) and sodium azide (NaN₃, O₂¹ species) were separately added to flasks containing organic contaminants (50.0 mL). The solutions without quenching agents were taken as controls. The solutions were exposed to visible light (120 min) followed by analysis using a UV–visible spectrophotometer. In Supplementary Text S5, instructions are provided for calculating the chemical oxygen demand (COD) of solutions containing nitroaromatic compounds both before and after photodegradation.

The reusability of the synthesized ferrite NPs was determined by performing five consecutive cycles of the photocatalysis process. In this experiment, the photocatalyst (0.1 g) was added to a 10 mL solution containing 0.5 mg/L of p-nitrophenol, pendimethalin and 0.05 mg/L of Martius yellow, respectively. To achieve adsorption–desorption equilibrium, the solutions were agitated for two hours at 130 rpm before being exposed to visible light. After 2 h, the centrifugation was carried out and the centrifugates were examined for the concentrations of residual concentrations of nitroaromatic contaminants. Following each photocatalytic cycle, the spent photocatalyst was repeatedly washed with deionized water. Finally, the photocatalysts were collected by magnetic separation and oven dried at 65 °C. The experiments were carried out three times and the mean values are reported.

3. Results and Discussion

3.1. Characterization

3.1.1. Structural Analysis

The XRD patterns of Sr_1−xTi_xFe₂O_4+δ (x = 0.0–1.0) NPs are given in Figure 1 and the calculated parameters are given in Table 1. Figure 1(aI) suggests the spinel structure of SrFe₂O₄ with the diffraction peaks at 2θ = 30.3, 35.7, 37.3, 43.4, 57.4, and 63.0, which were ascribed to the (220), (311), (222), (400), (333) and (440) Miller planes, respectively. The observed XRD peaks for SrFe₂O₄ match with the standard ICDD card no. 00-001-1027 and JCPDS card no. 08–0234 without any additional crystalline peak, corroborating the phase purity. The diffraction peaks of Figure 1(aII) indexed to the pure pseudobrookite-phase TiFe₂O₅ with an orthorhombic structure, in agreement with JCPDS card no. 87-1996. The XRD patterns of Ti⁴⁺-substituted SrFe₂O₄ NPs (Figure 1(aIII,aIV)) have all shown diffraction peaks of SrFe₂O₄ with an additional peak at 2θ = 32.6, corresponding to an increasing TiFe₂O₅ phase with the increased Ti⁴⁺ content. Additionally, the small monotonic shift was noticed for the strongest peak at a (311) Miller plane from 2θ = 35.7 to 36.4 with the increase in Ti⁴⁺ substitution in SrFe₂O₄ NPs (Figure 1b). Mansour et al. [36] also observed the shift of the (311) peak toward lower 2θ values with the Sm³⁺ substitution in Mg-Zn ferrites.

The lattice constant (a) was determined according to the following expression:

$a=\frac{d}{{(h^2+k^2+l^2)}^{1/2}}$

where a = lattice constant, d = full width at the half maximum and (hkl) = Miller planes. The decrease in lattice parameter can be described using Vegard’s law as the smaller radius of the dopant ion compared to the replacing ion favored lattice shrinkage and the lattice constant (a) decreased. The observed decrease in the lattice constant with increased Ti⁴⁺ content suggested the substitution (Figure S1). These findings are in good agreement with the results reported by Amaliya et al. [37] and Rao et al. [38] for Ti⁴⁺-doped cobalt ferrite.

Figure S1 demonstrated a steady reduction in X-ray density with the enhanced Ti⁴⁺ content because of the displacement of Sr²⁺ ions by Ti⁴⁺ ions of lower atomic weight. The lattice distortion caused by the ionic radii difference between the Ti⁴⁺ dopant (0.67 A) and Sr²⁺ ions (1.18 A) resulted in the reduction in crystalline size from 36.22.8 to 23.81.8 nm (Table 1). The presence of an excessive positive charge because of the Ti⁴⁺ dopant can be compensated for either by the generation of cationic vacancies or by oxygen non-stoichiometry that decreases the structure mobility, which results in smaller crystallite size [39]. The presence of oxygen hyerstoichiometry (δ) was confirmed by iodometric titrations [35].

The δ values of 0.0, 0.3, 0.6 and 1.0 with the reproducibility of 0.005 were observed for Sr_1−xTi_xFe₂O_4+δ (x = 0.0–1.0), respectively. The increased oxygen excess seen with increased content of Ti⁴⁺ ions in substituted ferrite NPs might be attributed to the generation of a larger number of cationic vacancies because of the displacement of divalent Sr²⁺ ions with tetravalent Ti⁴⁺ ions. The vacant lattice sites thus resulted in the oxygen excess. In Ti⁴⁺-substituted strontium ferrite NPs, the oxygen hyperstoichiometry and formation of cationic vacancies enhanced the photocatalytic properties by providing the heterogeneous surface to the nanomaterial. Furthermore, the existence of vacancies in substituted NPs could expand the valence band by creating the additional energy levels above it and consequently enhancing the charge separation and facilitating the transfer of photo-generated charge carriers (electrons and holes) to attain superior photocatalytic efficiency [40].

FT-IR spectra of pure and doped ferrite NPs depicted broad bands in the range of 3398–3466 cm⁻¹ (Figure 2(aI)) that were ascribed to O-H stretching vibrations of adsorbed H₂O molecules. The presence of prominent absorption bands in the region of 459–489 cm⁻¹ (Figure 2a,b) was attributed to metal–oxygen octahedral stretching modes, whereas the bands ranging between 534 cm⁻¹ and 606 cm⁻¹ matched to the tetrahedral M-O bond vibrations. The FT-IR spectra of the Ti⁴⁺-doped SrFe₂O₄ (Figure 2a (III and IV)) contained all the absorption bands of pristine SrFe₂O₄ NPs, but the positions of the bands corresponding to the M-O stretching vibrations (where M = Sr²⁺, Ti⁴⁺ and Fe³⁺) were shifted toward a higher-frequency region (Figure 2b) with the additional bands at 803 and 874 cm⁻¹ attributed to the O-Fe-O vibrations (Figure 2a). The shifting of the bands represented the change in the occupancy of the lattice sites by the smaller Ti⁴⁺ ions in the spinel lattice structure. The perturbation caused by the substitution of a smaller dopant ion led to reduced mass and increased force constant values. All these parameters favored the blue shift of M-O bands to a higher-frequency region.

3.1.2. Morphology, Surface Area and Magnetic Studies

The TEM micrograph of SrFe₂O₄ NPs demonstrated the non-uniform agglomerated NPs having an average diameter of 35–40 nm (Figure 3a and Figure S2a). The high agglomeration of SrFe₂O₄ might be ascribed to their high saturation magnetization values. The TEM image of TiFe₂O₅ showed the well-dispersed uniform NPs (Figure 3b and Figure S2b). The agglomeration extent was decreased on Ti⁴⁺ substitution, which could be ascribed to their decreased magnetic nature because of the introduction of non-magnetic Ti⁴⁺ ions (Figure 3c,d). The average particle diameter of the synthesized NPs was calculated from the histograms depicting particle-size distribution (Figure S2a–d). SEM micrographs of the pristine SrFe₂O₄ and TiFe₂O₅ NPs (Figure 3e,f) revealed agglomerated grains with discernible uneven grain boundaries consistent to the earlier results reported by Kaur et al. [41] and Pawar et al. [42] for the synthesis of ferrite NPs by the sol–gel method. The EDS spectra of substituted ferrites showed the effective atomic concentrations of different constituents (Sr, Ti, Fe and O) as depicted in Figure 3f,g. The peak intensity of the elemental peaks in the EDS spectra represented the concentration levels of the elements in the sample. Peak height correlated with the content of Ti⁴⁺ and Sr²⁺ ions. The large atomic percentage of Ti⁴⁺ and O²⁻ ions in Sr_0.4Ti_0.6Fe₂O_4.6 as compared to Sr_0.7Ti_0.3Fe₂O_4.3 confirmed the successful synthesis of oxygen hyperstoichiometric spinel ferrite NPs (Figure 3g,h).

The VSM plots (Figure 4a) displayed s-shaped hysteresis loops for synthesized ferrite NPs. The obtained magnetic parameters, viz. saturation magnetization (M_s), retentivity (M_r) and coercivity (H_c), are tabulated in Table 2. The M_s values are concerned with antiparallel magnetic interactions amongst the magnetic moments of cations existing at the O_h and T_d sites. The magnetic properties of SrFe₂O₄ being a mixed spinel ferrite are based on the site occupancy of different cations in its lattice structure. SrFe₂O₄ NPs had the highest M_s value (27.0 emu/g), revealing its promising magnetic properties, while TiFe₂O₅ had the lowest M_s value. In the case of Sr_1−xTi_xFe₂O_4+δ (x = 0.3 and 0.6), the magnetic moment decreased from 15.1 to 9.3 with an increase in the content of non-magnetic Ti⁴⁺ ions. This result might be attributed to the presence of a TiFe₂O₅ phase in doped samples and to the insertion of non-magnetic Ti⁴⁺ ions in SrFe₂O_4+δ, which reduced its ferrimagnetism and resulted in the decrease in the M_s value (Figure 4b). To ascertain the phase purity, we performed Mossbauer studies on pure and doped strontium ferrite. The Mossbauer results clearly demonstrated that doped ferrite had only a single phase as it displayed two sextets for the octahedral and tetrahedral sites of the spinel ferrite structure.

The increasing Ti⁴⁺ content also resulted in a regular decrease in H_c as a result of the decreased magnetocrystalline anisotropy constant (Figure 4b). Despite the decrease in magnetism, the ternary Sr_1−xTi_xFe₂O_4+δ NPs could still be successfully separated from the reaction solution by using an external magnet (Figure 4a (inset)).

Nitrogen adsorption–desorption isotherm models and Barnet–Joyner–Haleneda (BJH) curves were plotted to evaluate the specific surface area and pore size of synthesized NPs (Table 2). The observed isotherms (Figure 5a–d) could be classified as type –IV for all the NPs with an H3- hysteresis loop for SrFe₂O₄ and TiFe₂O₅ and an H4- hysteresis loop for Sr_0.7Ti_0.3Fe₂O_4.3 and Sr_0.4Ti_0.6Fe₂O_4.6 on the basis of Brunauer–Deming–Deming–Teller classification. The type-IV isotherm indicated the monolayer–multilayer adsorption associated with capillary condensation in mesoporous NPs. The hysteresis loop with type H3 corresponded to a wide distribution of pore sizes, whereas type H4 presented the typical mesoporous surface conditions. The Brunaure–Emmett–Teller (BET) specific surface area for SrFe₂O₄, TiFe₂O_5, Sr_0.7Ti_0.3Fe₂O_4.3 and Sr_0.4Ti_0.6Fe₂O_4.6 were ranged from 31.28 to 77.62 m²/g (Table 2). Thus, the Ti⁴⁺ substituents might increase the surface area of pristine SrFe₂O₄ NPs. This can be ascribed to the insertion of small-sized high-valence Ti⁴⁺ ions in the lattice sites of Sr²⁺ ions, thus generating vacancies and an increase in the heterogeneous mesoporous surface area during the sol–gel preparation period. The pore size distribution curves of bi-metallic and tri-metallic ferrite NPs exhibited sharp narrow peaks with pore size ranging from 3.61 to 3.63 nm, indicating their mesoporous nature. The pore volume was observed to be in the range of 0.04–0.07 cm³/g. The relatively higher specific surface area and mesoporous structure as compared to pristine SrFe₂O₄ could be considered as the favorable feature for the fast diffusion of pollutant molecules and this might increase the photocatalytic performance.

3.1.3. Mössbauer Studies

The Mössbauer spectra of Sr_1−xTi_xFe₂O_4+δ (x = 0.0–1.0) recorded at 25 °C are given in Figure 6 and the Mössbauer parameters are tabulated in Table 3. The ⁵⁷Fe Mössbauer spectra of SrFe₂O₄ NPs at room temperature displayed two sextets because of spinel phase. The sextets corresponded to the distinctive T_d (A) and O_h (B) sites, and the isomer shift values of 0.3 and 0.4 mm/s indicated the existence of Fe in a +3 oxidation state. The appearance of a quadruple doublet with IS and QS of 0.3 and 0.6 mm/s, respectively, indicated the presence of superparamagnetic particles. The higher isomer shift for the B site than the A site was because of more bond separation of Fe³⁺–O²⁻ for O_h ions than T_d ions. As a result of this, the reduced overlapping between the Fe³⁺ and O²⁻ ions’ orbitals led to the smaller covalence effect, which was responsible for a larger isomer shift at the O_h sites. The Mössbauer spectrum of TiFe₂O₅ reveals two doublets with isomer shifts of 0.4 and 0.3 mm/s demonstrating the presence of iron ions in a Fe³⁺ state. The IS change was insignificant with the increasing concentration of Ti⁴⁺ ions. The observed results reveal that s-electron density at the Fe³⁺ nucleus remains unaltered with Ti⁴⁺ substitution. Similar insignificant changes of isomer shift were observed by Chand et al. [43] and Chongtham et al. [44] with the increasing content of Ti⁴⁺ ions in NiFe₂O₄. The small quadruple splitting values observed in the Mössbauer spectra of Sr_1−xTi_xFe₂O_4+δ (x = 0.3 and 0.6) indicated only slight shifts of Ti⁴⁺ ions on both the T_d and O_h sites. The consistent small quadruple splitting values were obtained by Kale et al. [45] for the Ni_1+xTi_xFe_2−2xO₄ (0.0 × 0.7). The quadrupole interaction ascribed to the superparamagnetic nanoparticles, i.e., TiFe₂O₅, was observed to be different. The spectral view of this phenomenon has been demonstrated by the presence of the two quadruple doublets. These different quadruple splitting values for the similar isomer shift values indicate the presence of small ferrite nanoparticles with different sizes that undergo superparamagnetic relaxation at room temperature. A similar phenomenon was observed by Kassabova-Zhetcheva et al. [46] for Mg_xZn_1−xFe₂O₄ nanoparticles.

The nuclear magnetic field is regulated by the Fermi-contact interactions between the spin-polarized shells of s-electrons and the nucleus, which is significantly influenced by a little change in the s-electron density consequential from the variation in the cationic environment. The internal magnetic field did not show discernible change corresponding to both the sextets in the present study because of insignificant changes in the isomer shift. The tetravalent Ti⁴⁺ ions are non-magnetic and, thus, cannot contribute to the net magnetic field. Therefore, the net magnetic field results from the interactions between the Fe³⁺ ions at the A and B sites and depends primarily on the strength and number of the superexchange Fe³⁺_A–O²⁻–Fe³⁺_B bonds. Thus, no change was observed in H_A and H_B on Ti⁴⁺ substitution.

3.1.4. Optical Studies

The optical behavior was comparatively analyzed from the band gap and photoluminescence studies of the pristine and doped ferrite NPs. The band gap energy (E_g) defines the energy essential to excite the valence electron to conduction band (CB) from the valence band (VB), which serves as charge carrier for the photocatalytic applications. To evaluate E_g, the most widely used method, i.e., the Tauc plot method, was used. The general equation of the Tauc plot method is given in Equation (3).

(αhν)= A(hν − E_g)ⁿ(3)

where A = energy-dependent constant, α = absorption constant, hν = incident energy of photon, E_g = band gap energy and n depends on the nature of electronic transition and is 0.5 and 2.0 for indirect and direct E_g, respectively [47,48]. The direct E_g is based on the assumption of direct transition between the edges of VB and CB. In the present study, the ferrite NPs showed a linear plot in the graph of (αhν)² vs. hν. So, the direct E_g values were evaluated by extrapolating the linear part of the curve. TiFe₂O₅ NPs revealed the highest E_g with a value of 2.45 eV, whereas the pristine SrFe₂O₄ NPs displayed an E_g of 2.34 eV (Figure 7a). Among the Ti⁴⁺ substituted ferrite NPs, the Sr_0.4Ti_0.6Fe₂O_4+δ NPs with high Ti⁴⁺ content showed greater reduction in E_g from 2.34 to 2.18 eV. The narrowing of E_g values can be ascribed to the defects produced by the introduction of Ti⁴⁺ dopant ions, which led to the presence of new energy levels between VB and CB. The reduction in band gap is consistent to the observations reported by Singh et al. [31] for Ti⁴⁺-doped magnesium ferrite NPs. However, the lower obtained band gap in the present study may be due to the electron confinement effect that resulted in the more feasible transfer of electrons to the CB from VB in Sr_0.4Ti_0.6Fe₂O_4.6. Thus, the reduction in band gap on Ti⁴⁺ substitution in SrFe₂O₄ resulted in an enhanced photocatalytic potential for their application in the degradation of organic contaminants under visible-light illumination.

The fluorescence studies in the wavelength range of 200–700 nm were conducted as shown in Figure 7b. The photoluminescent spectra exhibited a broader emission band centered at 410 nm, which is ascribed to the photoinduced e⁻₋ h⁺ pair recombination. This band might be caused by the presence of radiative, structural and surface defects and assigned to d-d transitions in Fe³⁺ ions [49]. The intensities of the PL emission band centered at 410 nm became reduced with an increase in the Ti⁴⁺ content in SrFe₂O₄, which was due to the presence of discrete energy levels between the VB and CB as a result of intrinsic defects. The lowering of luminous intensity was also observed for the Ce³⁺-doped strontium ferrite, La³⁺- and Se³⁺-doped bismuth ferrite, Sr²⁺-doped zinc ferrite and Eu³⁺-doped magnesium ferrite NPs [50,51,52,53]. In the present study, the photoluminescent emissions decreased in the following order:

TiFe₂O₅ > SrFe₂O₄ > Sr_0.7Ti_0.3Fe₂O_4.3 > Sr_0.4Ti_0.6Fe₂O_4.6.

The lowering of PL intensity on Ti⁴⁺ substitution indicates the inhibition of charge carriers’ recombination, which favored the observed higher photocatalytic activity of Sr_0.4Ti_0.6Fe₂O_4.6 NPs. The higher fluorescence quenching, low band gap values and higher specific surface area of Sr_0.4Ti_0.6Fe₂O_4.6 NPs have made them more advantageous than Ti⁴⁺-doped magnesium ferrite NPs.

3.1.5. Capacitance–Voltage (C-V) Measurement

The capacitance–voltage dependence was studied in the Schottky barrier diode of Al/Sr_1−xTi_xFe₂O_4+δ (x = 0.0, 0.3, 0.6 and 1.0) ferrite at a constant frequency of 100 KHz under reverse-bias voltage (Figure 7c). The details of the Schottky diode are given in Text S6. Under reverse biasing, a zone of uncovered charge that contributes to the development of the depletion region and establishes the depletion width forms on one side of the Schottky junction. The width of the depletion region grows as the reverse-bias potential rises and, as a result, lowers the capacitance [54]. Figure 7d depicts the graph of 1/C² versus reverse-bias voltage (V) for pure and TI⁴⁺-doped synthesized Sr_1−xTi_xFe₂O_4+δ (x = 0.0, 0.3, 0.6 and 1.0) ferrite NPs. Each plot satisfied a linear relation. C-V parameters, viz. carrier concentration (N_D), barrier height (Φ_b) and built-in voltage (V_bi), are determined using the equations given in Table S1. The calculated parameters are given in Table 4. The linear portion is extrapolated with voltage axis in Figure 7d. The Φ_b kept on decreasing with the increased Ti⁴⁺ content for Sr_1−xTi_xFe₂O_4+δ, which was well-concordant with the decreased band gap values determined from the Tauc plot (Figure 7a).

4. Photocatalytic Degradation Studies

4.1. Effect of pH and Photocatalyst Dose

The photocatalytical efficiency is largely dependent on the solution pH as it affects the charge on the surface, adsorption–desorption equilibrium and ionization of organic pollutants. In addition to it, the pH of solution can also influence the production of active oxygen (e.g., O₂^●− and ^●OH) in photocatalytical processes. The pH at zero-point charge (pH_ZPC) and zeta potential values were evaluated to examine the surface charge of synthesized photocatalysts. The effect of pH on photodegradation is presented in Figure 8a and Figure S3a–f. The control experiment, only under light irradiation without a photocatalyst, was performed to rule out the possibility of the nitroaromatics’ photodegradation because of photolysis, which was shown to be insignificant (Figure 8a and Figure S3a–e). Another control trial for the batch of the nitroaromatics’ solution treated with synthesized pristine and Ti⁴⁺-substituted ferrite NPs under dark conditions also revealed insignificant removal (Figure S3f). This clearly reflected that the adsorption of the studied nitroaromatic pollutants is negligible. The negative results of the control experiments revealed that the removal of nitroaromatic pollutants was neither due to their adsorption on photocatalysts nor due to photolysis. It might be summarized from the results that the removal was solely because of photodegradation by NPs. Moreover, the solutions of nitroaromatics in the presence of H₂O₂ without a photocatalyst demonstrated less than 24.2 ± 1.5% degradation of studied nitroaromatic compounds, which is inefficient. However, the combination of photocatalysts with H₂O₂ in the presence of visible-light exposure increased the photodegradation efficiency ranging from 86.2 ± 1.6% to 94.2 ± 0.8%. The photoinduced e⁻ on the photocatalyst surface reacts with H₂O₂, an electron acceptor, to produce reactive oxygen species and is vital for the higher photodegradation of model pollutants [55,56]. Under acidic conditions, the photocatalytical degradation of the three studied nitroaromatic pollutants was higher under the illumination of visible light (Figure 8a and Figure S3a,b) than ultraviolet light (Figure S3c–e). This was attributed to the visible range E_g of the synthesized NPs. At pH 3.0 and under visible-light illumination, a superior photocatalytical performance was obtained for Sr_0.4Ti_0.6Fe₂O_4.6 NPs than the other photocatalysts, with percentage removals of 91.3, 94.4 and 87.2% for p-nitrophenol, pendimethalin and Martius yellow, respectively. This might be correlated to the production of greater reactive oxygen species at an acidic pH [57]. The measurements of ξ- potential (Figure 8b, Table 1) and pH_ZPC (Figure 8c) values further supported the observed results. The respective pH_ZPC values for SrFe₂O₄, TiFe₂O₅, Sr_0.7Ti_0.3Fe₂O_4.3 and Sr_0.4Ti_0.6Fe₂O_4.6 NPs were 6.2, 5.8, 5.2 and 4.8, respectively (Figure 7d). At pH pH_ZPC, a positive surface charge may be related to the protonation of hydroxyl groups on the surface of the photocatalysts. Furthermore, the surface potential at pH 3.0 was observed to be more positive for Sr_0.4Ti_0.6Fe₂O_4.6 NPs (32.41 mV) as compared to other photocatalysts, causing greater electrostatic attractions among anionic nitroaromatic compounds and the protonated surface of the Sr_0.4Ti_0.6Fe₂O_4.6 NPs. Thus, the optimum pH for the photodegradation of the studied pollutants using Sr_0.4Ti_0.6Fe₂O_4.6 NPs was 3.0.

The generation of cationic vacancies and oxygen hyperstoichiometry in the Sr_0.4Ti_0.6Fe₂O_4.6 NPs are expected to enhance the photocatalytic properties by providing the heterogeneous surface to the nanomaterial. Additionally, the vacant sites created by the insertion of Ti⁴⁺ ions in the SrFe₂O₄ lattice aided the trapping of e⁻-h⁺ pairs and consequently lowered their recombination rate. The existence of vacant sites in substituted NPs might expand the VB by generating additional energy levels above it and subsequently enhancing the charge separation and facilitating the diffusion of photo-generated charge carriers to achieve greater photocatalytic efficiency. This was corroborated to the results reported by Ai et al. [40]. Their outstanding photocatalytic efficiency was further substantiated by their high specific surface area (77.6 m²/g), as determined using BET analysis. The higher photocatalytic efficiency of Sr_0.4Ti_0.6Fe₂O_4.6 NPs could also be ascribed to the reduction in E_g with the generation of some impurity levels above the VB and below the CB of photocatalytic system with Ti⁴⁺ substitution. Chen et al. [12] also reported the formation of additional levels between VB and CB caused by the presence of La/N co-dopants in TiO₂. The Ti⁴⁺ substituents acted as electron acceptors because of the more positive charge on them, thus preventing the recombination of photo-generated e⁻ and h⁺ pairs and consequently leading to the improvement of photocatalytic degradation. The red shift observed in E_g values also indicated the increased photon numbers by extending the energy range of photoexcitation, which can be absorbed by the photocatalyst and utilized for photocatalytic reaction. The work is consistent to the studies reported by Khosravi et al. [58]. These studies displayed the Sr_0.4Ti_0.6Fe₂O_4.6 NPs as the best photocatalyst and, hence, it was used for conducting the further studies.

The details of the photocatalyst dose are explained in Text S7. The photodegradation efficiency increased when the photocatalyst dose increased from 0.01 g/L to 0.2 g/L for p-nitrophenol and pendimethalin and up to 0.4g/L for Martius yellow. This might be due to more surface area being available, which resulted in enhanced photocatalytic sites [59] (Figure S4d).

4.2. Kinetic Studies

The photocatalytic potential of Sr_0.4Ti_0.6Fe₂O_4.6 NPs for p-nitrophenol, pendimethalin and Martius yellow was studied under visible-light illumination. The temporal UV–visible spectra of nitroaromatic pollutants are illustrated in Figure 9a–c. With the progress of the reaction, the absorption maxima for the pollutants decreased, signifying their degradation. The appearance of a new peak at 290 nm in the case of p-nitrophenol further supported its degradation caused by the formation of hydroquinones [60,61]. The decolorization of the solution might be caused by the result of de-nitration of the chromophoric ring, thus revealing the change in the molecular configuration.

The kinetics of photodegradation followed the first-order reaction model as indicated from the linear relationship (R² 98%) in the curves obeying the Langmuir–Hinshelwood model (Figure 10a,b and Figure S4a–c). The values of apparent rate constant (k) of Sr_1−xTi_xFe₂O_4+δ ferrite NPs (x = 0.0–1.0) for the quantitative evaluation of photodegradation were calculated and are given in Table 5. The evaluated k values were observed to be the highest for Sr_0.4Ti_0.6Fe₂O_4.6 NPs among the synthesized photocatalysts (Table 5). The higher k values clearly represent the faster photocatalytic reaction in the presence of Sr_0.4Ti_0.6Fe₂O_4.6 NPs. This trend could be supported by the highest positive surface charge of Sr_0.4Ti_0.6Fe₂O_4.6 NPs (see value sof ξ- potential and pH_ZPC measurements). Moreover, among the studied nitroaromatic compounds, the maximum value of k was found to be 2.31 × 10⁻² min⁻¹ for pendimethalin as compared to p-nitrophenol (1.95 × 10⁻² min⁻¹) and Martius yellow (1.32 × 10⁻² min⁻¹) for Sr_0.4Ti_0.6Fe₂O_4.6 NPs. The low apparent constant value for Martius yellow might be ascribed to its more stable structure because of the resonance of two aromatic rings [62]. Slower degradation of p-nitrophenol as compared to pendimethalin might be due to the resonance stabilization of the p-nitrophenolate ion.

4.3. Identification of Active Species and Photocatalytic Mechanism

The photodegradation mechanism of nitroaromatic pollutants using Sr_0.4Ti_0.6Fe₂O_4.6 NPs was examined by applying specific reactive oxygen species quenching agents in the solutions comprising the nitroaromatic solution and Sr_0.4Ti_0.6Fe₂O_4.6 NPs. The Langmuir–Hinshelwood studies of photodegradation of nitroaromatic pollutants in the presence of methanol, ethylene diamine tetraacetate (EDTA), sodium azide and ascorbic acid are shown in Figure 11a–c. The rate of inhibition of photodegradation of the studied nitroaromatic compounds for the batch treated with ascorbic acid was significantly more. It indicated that the generation of superoxide anion radicals (O₂^•−) was significant for Sr_0.4Ti_0.6Fe₂O_4.6 NPs. Singlet oxygen species (O₂¹) are generated because of the reaction of holes with O₂^•− [63]. In the batch treated with an addition of sodium azide, EDTA and methanol, the modest inhibition of the photodegradation rate was also observed. It implied that O₂¹, h⁺ and ^•OH radicals also had the effect in the photocatalytical degradation of nitroaromatic compounds. The decreased inhibition in the dye degradation rate was also reported using sodium azide as a scavenging agent using Se-doped ZnS NPs by Talukdar et al. [64]. The role of reactive oxygen species in the photodegradation process was observed to be in following order:

Superoxide radical anions singlet oxygen species holes hydroxyl radicals

To comprehend the insight mechanism underlying the separation of e⁻ and h⁺, the potential of Sr_0.4Ti_0.6Fe₂O_4.6 associated with VB and CB was determined as [2,65]:

E_CB = χ − E_ef − 0.5 E_g(4)

E_VB = E_CB + E_g(5)

where χ (arithmetic mean of atomic electron affinity and their first ionization energy), E_VB = VB edge potential, E_CB = CB edge potential, E_g = band gap energy of semiconductor and E_ef = free electrons energy (e⁻) on the standard hydrogen scale (4.5 eV).

The electronegativity value for Sr_0.4Ti_0.6Fe₂O_4.6 was calculated to be 5.23 eV. The determined E_VB and E_CB for Sr_0.4Ti_0.6Fe₂O_4.6 NPs were −0.31 eV and +1.79 eV, respectively, as given in Figure 9e. The E_VB of Sr_0.4Ti_0.6Fe₂O_4.6 is 1.79 eV vs. NHE, which is less than the E (^–OH/•OH) redox potential (1.99 eV vs. NHE) [17]. Therefore, valence h⁺ created in Sr_0.4Ti_0.6Fe₂O_4.6 cannot interact with H₂O or ⁻OH to generate highly reactive oxygen species (•OH). However, the E_CB of Sr_0.4Ti_0.6Fe₂O_4.6 is—0.31 eV vs. NHE, respectively, which is more than the E (O₂/O₂^•−) redox potential (−0.046 eV vs. NHE) [66,67] to reduce O₂ to O₂^•−. These O₂^•− can capture H₂O to further form •OH radicals [56,66]. The reactive oxygen species, viz. O₂^•− and •OH, thus formed are capable of oxidizing nitroaromatic pollutants and mineralizing them. The low band gap (2.18 eV) of Sr_0.4Ti_0.6Fe₂O_4.6 NPs facilitated the electron excitation when exposed to visible light (Equation (6)) (Figure 12). The narrowing of the band gap might be because of the intrinsic energy levels with the substitution of Ti⁴⁺ in SrFe₂O₄. The accumulation of photo-generated electrons increased on the CB and photocatalytic active sites were generated on the photocatalyst’s surface. The holes (h⁺) reacted with the H₂O molecules from the reaction medium to form ^•OH (Equation (7)). The photo-induced electrons (e⁻), on reacting with dissolved O₂, get transformed into O₂^•− (Equation (8)). The O₂^•−, on reacting with H⁺ ions, generates peroxyl radicals (•OOH) (Equation (9)). O₂^•− on reaction with holes could generate singlet oxygen species (O₂¹) (Equation (10)). The OOH radicals consequently decompose to produce the •OH and O₂^•− radicals (Equations (11)–(13)). These reactive oxygen species could target the nitroaromatic pollutants and mineralize them into degraded products (Equation (14)).

(6)${\mathrm{Sr}}_{0.4}{\mathrm{Ti}}_{0.6}{\mathrm{Fe}}_2{\mathrm{O}}_{4.6}+\mathrm{hv} \stackrel{\hspace{1em}\hspace{1em}}{\to }{ \mathrm{Sr}}_{0.4}{\mathrm{Ti}}_{0.6}{\mathrm{Fe}}_2{\mathrm{O}}_{4.6} \left({\mathrm{e}}^{-}{}_{\mathrm{CB}}+{\mathrm{h}}^{+}{}_{\mathrm{VB}}\right)$

(7)${\mathrm{Sr}}_{0.4}{\mathrm{Ti}}_{0.6}{\mathrm{Fe}}_2{\mathrm{O}}_{4.6} \left({\mathrm{h}}^{+}{}_{\mathrm{VB}}\right)+{\mathrm{H}}_2\mathrm{O} \stackrel{\hspace{1em}\hspace{1em}}{\to }{ \mathrm{HO}}^{•}$

(8)${\mathrm{Sr}}_{0.4}{\mathrm{Ti}}_{0.6}{\mathrm{Fe}}_2{\mathrm{O}}_{4.6} \left({\mathrm{e}}^{-}{}_{\mathrm{VB}}\right)+{\mathrm{O}}_2\underset{\hspace{1em}\hspace{1em}}{\to }{ \mathrm{O}}_2{}^{•-}$

(9)${\mathrm{O}}_2{}^{•-}+{\mathrm{H}}^{+} \stackrel{\hspace{1em}\hspace{1em}}{\to }{ \mathrm{HOO}}^{•}$

(10)${\mathrm{O}}_2{}^{•-}+{\mathrm{h}}^{+}{}_{\mathrm{VB}}\stackrel{\hspace{1em}\hspace{1em}}{\to }{ \mathrm{O}}_2{}^1$

(11)${\mathrm{HO}}^{•}+{\mathrm{HOO}}^{•}\stackrel{\hspace{1em}\hspace{1em}}{\to }{ \mathrm{H}}_2{\mathrm{O}}_2+{\mathrm{O}}_2$

(12)${\mathrm{H}}_2{\mathrm{O}}_2+{\mathrm{O}}_2{}^{-•}\stackrel{\hspace{1em}\hspace{1em}}{\to }{ \mathrm{HO}}^{•}+{\mathrm{HO}}^{-}$

(13)${\mathrm{H}}_2{\mathrm{O}}_2+{\mathrm{e}}^{-}{}_{\mathrm{CB}}\stackrel{\hspace{1em}\hspace{1em}}{\to }{ \mathrm{HO}}^{•}+{\mathrm{HO}}^{-}+{\mathrm{O}}_2{}^{-•}$

(14)${\mathrm{OH}}^{-}{/\mathrm{h}}^{+}{/\mathrm{O}}_2{{}^{-}}^{•}+\mathrm{Organic} \mathrm{pollutants} \stackrel{\hspace{1em}\hspace{1em}}{\to } \mathrm{Degraded} \mathrm{products}+{\mathrm{CO}}_2+{\mathrm{H}}_2\mathrm{O}$

The photocatalytic results were also authenticated by calculating the COD of nitroaromatic compounds, which decreased to 20.7 mg/L (p-nitrophenol), 27.4 mg/L (pendimethalin) and 26.0 mg/L (Martius yellow) after photodegradation using Sr_0.4Ti_0.6Fe₂O_4.6 NPs from initial value of 54.8 mg/L, 61.7 mg/L and 58.3 mg/L, respectively.

4.4. Reusability Studies

The stability and reusability of the Sr_0.4Ti_0.6Fe₂O_4.6 NPs were investigated by conducting photodegradation experiments five times. The Sr_0.4Ti_0.6Fe₂O_4.6 NPs were separated and thoroughly washed with deionized water after each photocatalytic cycle, and fresh solutions of the three studied nitroaromatic pollutants were used before the successive photocatalytic run in the presence of visible light. Figure 10c displayed that the photodegradation ability of these nitroaromatic compounds decreased slightly, ranging from 7 to 9% even after the fifth photocatalytic cycle. This suggested the excellent regeneration of Sr_0.4Ti_0.6Fe₂O_4.6 in the photocatalytic degradation of nitroaromatic pollutants.

5. Conclusions

Significant variations in structural and optical properties were observed with Ti⁴⁺ substitution in the strontium ferrite. Optical and capacitance studies confirmed the superior photocatalytic potential of Sr_0.4Ti_0.6Fe₂O_4.6 as compared to synthesized pristine ferrite NPs. The photodegradation efficiency of pristine SrFe₂O₄ NPs ranges from 63% to 78% and it increased significantly to 87–94% for Sr_0.4Ti_0.6Fe₂O_4.6 NPs. The efficient photocatalytic performance of Sr_0.4Ti_0.6Fe₂O_4.6 NPs could be related to the generation of cationic vacancies, enhanced surface area, lowering of band gap and photoluminescence intensity in the doped ferrite. Capacitance studies affirmed that Ti⁴⁺ substitution caused an increase in the charge carrier concentration and lowering of barrier height. The observed results suggested the potential of trimetallic Sr_0.4Ti_0.6Fe₂O_4+δ NPs as a promising photocatalyst for organic pollutants. Tuning the composition of oxygen hyperstoichiometric Ti⁴⁺-substituted strontium ferrite is a promising strategy for improving the effectiveness of strontium-ferrite-based photocatalysts.

Author Contributions

J.K.G.: data curation, methodology, writing—original draft, writing—review and editing. M.K.: writing—original draft, writing—review and editing, supervision. R.K.S.: validation, formal analysis and editing. A.C.O.: validation, formal analysis and editing. V.K.G.: validation, formal analysis and editing. V.K.S.: writing—review and editing, supervision. All authors have read and agreed to the published version of the manuscript.

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

Data will be made available upon reasonable request.

Conflicts of Interest

The authors declare no conflict of interest.

Publisher’s Note: MDPI stays neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Figures and Tables

Figure 1. (a) XRD patterns, (b) enlarged view of peak shift position of the (311) Bragg peak of (I) SrFe2O4, (II) TiFe2O5, (III) Sr0.7Ti0.3Fe2O4.3 and (IV) Sr0.4Ti0.6Fe2O4.6 (Dotted black line represents the location of (311) Bragg peak for SrFe2O4 NPs).

Figure 2. (a) FT-IR spectra of (I) SrFe2O4, (II) TiFe2O5, (III) Sr0.7Ti0.3Fe2O4.3 and (IV) Sr0.4Ti0.6Fe2O4.6 and (b) enlarged view of the peak shift position of metal–oxygen FT-IR peaks (Dotted red line represents the location of metal–oxygen tetrahedral and octahedral stretching peaks for SrFe2O4 NPs).

Figure 3. TEM and SEM-EDS images of (a,e) SrFe2O4, (b,f) TiFe2O5, (c,g) Sr0.7Ti0.3Fe2O4.3 and (d,h) Sr0.4Ti0.6Fe2O4.6..

Figure 4. (a) Hysteresis curves of (I) SrFe2O4, (II) Sr0.7Ti0.3Fe2O4.3 (III) Sr0.4Ti0.6Fe2O4.6 and (IV) TiFe2O5, magnetic separation of Sr0.4Ti0.6Fe2O4.6 (inset); (b) variation of saturation magnetization and coercivity; (c) variation of surface area and pore diameter.

Figure 5. BET isotherm curves of (a) SrFe2O4, (b) TiFe2O5, (c) Sr0.7Ti0.3Fe2O4.3 and (d) Sr0.4Ti0.6Fe2O4.6.

Figure 6. Mössbauer spectra of (I) SrFe2O4, (II) Sr0.7Ti0.3Fe2O4.3, (III) Sr0.4Ti0.6Fe2O4.6 and (IV) TiFe2O5.

Figure 7. (a) Tauc plot and (b) photoluminescence spectra, (c) capacitance–voltage diagram and (d) (1/Capacitance)2 versus reverse-bias voltage of (I) SrFe2O4, (II) TiFe2O5, (III) Sr0.7Ti0.3Fe2O4.3 and (IV) Sr0.4Ti0.6Fe2O4.6 NPs.

Figure 8. (a) Photocatalytic degradation of (a) p-nitrophenol under visible-light irradiation (experimental conditions: catalyst dose, 0.2 g/L; irradiation time, 2 h) (b) Zeta potential curve and (c) pHZPC of synthesized Sr1−xTixFe2O4+δ (x = 0.0—1.0) ferrite NPs.

Figure 8. (a) Photocatalytic degradation of (a) p-nitrophenol under visible-light irradiation (experimental conditions: catalyst dose, 0.2 g/L; irradiation time, 2 h) (b) Zeta potential curve and (c) pHZPC of synthesized Sr1−xTixFe2O4+δ (x = 0.0—1.0) ferrite NPs.

Figure 9. (a) Temporal curves for photocatalytic degradation of (a) p-nitrophenol, (b) pendimethalin and (c) Martius yellow (experimental conditions: pH, 3.0; catalyst dose, 0.2g/L and concentration, 0.5 mg/L (p-nitrophenol and pendimethalin), 0.05 mg/L (Martius yellow)).

Figure 10. (a) Effect of irradiation time, (b) Langmuir–Hinshelwood kinetic plots on photodegradation of nitroaromatic pollutants using Sr0.4Ti0.6Fe2O4.6 NPs and (c) desorption studies of p-nitrophenol, pendimethalin and Martius yellow (experimental conditions: pH, 3.0; temperature, 25.0 ± 1 °C; irradiation time, 2.0 h; catalyst dose, 0.2 g/L (p-nitrophenol and pendimethalin and 0.4 g/L (Martius yellow))).

Figure 10. (a) Effect of irradiation time, (b) Langmuir–Hinshelwood kinetic plots on photodegradation of nitroaromatic pollutants using Sr0.4Ti0.6Fe2O4.6 NPs and (c) desorption studies of p-nitrophenol, pendimethalin and Martius yellow (experimental conditions: pH, 3.0; temperature, 25.0 ± 1 °C; irradiation time, 2.0 h; catalyst dose, 0.2 g/L (p-nitrophenol and pendimethalin and 0.4 g/L (Martius yellow))).

Figure 11. Kinetic studies of inhibition of degradation of (a) p-nitrophenol, (b) pendimethalin and (c) Martius yellow (Experimental conditions: pH, 3.0; catalyst dose, 0.2 g/L (p-nitrophenol, pendimethalin) and 0.4 g/L (Martius yellow) and concentration 0.5 mg/L (p-nitrophenol and pendimethalin) and 0.05 mg/L (Martius yellow).

Figure 12. Plausible photodegradation mechanism for the photodegradation of nitroaromatic pollutants.

Table 1

XRD parameters, ξ- potential and DLS hydrodynamic particle size of SrFe₂O₄, TiFe₂O₅, Sr_0.7Ti_0.3Fe₂O_4.3 and Sr_0.4Ti_0.6Fe₂O_4.6.

Nanomaterial	LatticeConstant(A)	ExperimentalDensity (ρexp in g/cm3)	Crystallite Size (nm)	XRD Density(ρXRD in g/cm3)	% Porosity	ξ- Potential(mV)	DLS Hydrodynamic Particle Size (nm)
SrFe2O4	10.03 0.08	3.220.4	36.252.8	4.510.2	6.852.3	13.54	123.92
TiFe2O5	8.730.01	2.190.3	31.74	3.450.4	45.523.2	14.78	105.52
Sr0.7Ti0.3Fe2O4.3	9.150.02	2.870.3	27.212.7	4.280.4	36.362.6	23.54	101.79
Sr0.4Ti0.6Fe2O4.6	9.040.03	2.430.2	23.861.8	4.020.3	43.222.5	32.41	95.23

Table 2

BET and VSM parameters of SrFe₂O₄, TiFe₂O₅, Sr_0.7Ti_0.3Fe₂O_4.3 and Sr_0.4Ti_0.6Fe₂O_4.6.

Nanomaterial	Surface Area (m2/g)	Pore Volume (cm3/g)	Pore Diameter (nm)	Saturation MagnetizationMs (emug−1)	RetentivityMr (emug−1)	CoercivityHc (Oe)
SrFe2O4	44.28	0.035	3.616	27.03	0.0017	155.1
TiFe2O5	31.96	0.070	3.612	8.38	0.0015	72.4
Sr0.7Ti0.3Fe2O4.3	66.71	0.070	3.618	15.08	0.0043	141.4
Sr0.4Ti0.6Fe2O4.6	77.62	0.071	3.629	9.35	0.5963	82.6

Table 3

Mössbauer parameters of SrFe₂O₄, TiFe₂O₅, Sr_0.7Ti_0.3Fe₂O_4.3 and Sr_0.4Ti_0.6Fe₂O_4.6.

Nanomaterial	Isomer Shift(mm/s)	Q. Splitting(Δ, mm/s)	Magnetic Field(B, T)	Area (%)
SrFe2O4	0.40 $\pm$ 0.01 (S)	−0.10 $\pm$ 0.04	51.00 $\pm$ 0.16	16.20
	0.30 $\pm$ 0.01 (S)	0.10 $\pm$ 0.02	49.30 $\pm$ 0.30	41.60
	0.30 $\pm$ 0.00 (D)	0.60 $\pm$ 0.00	-	42.20
Sr0.7Ti0.3Fe2O4.3	0.40 $\pm$ 0.01 (S)	−0.10 $\pm$ 0.02	51.00 $\pm$ 0.18	16.20
	0.30 $\pm$ 0.00 (S)	0.10 $\pm$ 0.02	49.30 $\pm$ 0.19	41.60
	0.30 $\pm$ 0.00 (D)	0.60 $\pm$ 0.00	-	42.20
Sr0.4Ti0.6Fe2O4.6	0.40 $\pm$ 0.01 (S)	−0.10 $\pm$ 0.02	51.00 $\pm$ 0.17	16.20
	0.30 $\pm$ 0.01 (S)	0.10 $\pm$ 0.02	49.30 $\pm$ 0.17	41.60
	0.30 $\pm$ 0.00 (D)	0.60 $\pm$ 0.00	-	42.20
TiFe2O5	0.30 $\pm$ 0.00 (D)	0.60 $\pm$ 0.00	-	59.10
	0.30 $\pm$ 0.00 (D)	1.00 $\pm$ 0.01	-	40.90

Table 4

C-V parameters of Al/SrFe₂O₄, TiFe₂O₅, Sr_0.7Ti_0.3Fe₂O_4.3 and Sr_0.4Ti_0.6Fe₂O_4.6 ferrite Schottky diode.

Nanomaterial	Built in Voltage (V)	Barrier Height (eV)	Carrier Concentration (cm−3)
SrFe2O4	0.54	1.20	4.90 × 1015
TiFe2O5	0.49	1.15	6.05 × 1015
Sr0.7Ti0.3Fe2O4.3	0.42	1.10	6.52 × 1015
Sr0.4Ti0.6Fe2O4.6	0.32	1.02	6.96 × 1015

Table 5

Values of apparent rate constant and regression coefficient values for nitroaromatic compounds using SrFe₂O₄, TiFe₂O₅, Sr_0.7Ti_0.3Fe₂O_4.3 and Sr_0.4Ti_0.6Fe₂O_4.6 NPs.

Nanomaterial	Pollutant Name	Apparent Rate Constant Value (k, min−1)	R2-Value
SrFe2O4	p-nitrophenol	1.65 × 10−2 $\pm$0.001	0.99
	Pendimethalin	1.86 × 10−2$\pm$0.002	0.99
	Martius yellow	0.11 × 10−2$\pm$0.001	0.98
TiFe2O5	p-nitrophenol	1.54 × 10−2$\pm$0.001	0.99
	Pendimethalin	1.73 × 10−2$\pm$0.001	0.98
	Martius yellow	0.10 × 10−2$\pm$0.002	0.97
Sr0.7Ti0.3Fe2O4.3	p-nitrophenol	1.87 × 10−2$\pm$0.001	0.99
	Pendimethalin	1.95 × 10−2$\pm$0.001	0.99
	Martius yellow	0.11 × 10−2$\pm$0.003	0.99
Sr0.4Ti0.6Fe2O4.6	p-nitrophenol	1.95 × 10−2$\pm$0.001	0.98
	Pendimethalin	2.31 × 10−2$\pm$0.001	0.99
	Martius yellow	1.32 × 10−2$\pm$0.001	0.99

Supplementary Materials

The following supporting information can be downloaded at: https://www.mdpi.com/article/10.3390/magnetochemistry8100120/s1, Table S1. Equations used for the determination of C-V parameters; Scheme S1. Schematic representation of synthesis of oxygen hyperstoichiometric trimetallic titanium substituted strontium ferrite nanoparticles; Figure S1. Variation of XRD density lattice constant and XRD density with increasing Ti content; Figure S2. Histograms showing particle size distribution of (a) SrFe₂O₄, (b) TiFe₂O₅, (c) Sr_0.7Ti_0.3Fe₂O_4.3 and (d) Sr_0.4Ti_0.6Fe₂O_4.6 NPs; Figure S3. Photocatalytic degradation of (a) pendimethalin and (b) martius yellow under visible light irradiation and (c) p-nitrophenol, (d) pendimethalin and (c) martius yellow under ultraviolet light irradiation without catalyst, SrFe₂O₄, TiFe₂O₅, Sr_0.7Ti_0.3Fe₂O_4.3 and Sr_0.4Ti_0.6Fe₂O_4.6 NPs(Experimental conditions: catalyst dose, 0.2 g/L for p-nitrophenol and pendimethalin, 0.4 g/L for martius yellow; irradiation time, 2 h and concentration 0.5 mg/L (p-nitrophenol and pendimethalin) and 0.05 mg/L (Martius yellow); (f) Photocatalytic degradation of p-nitrophenol, pendimethalin and martius yellow without light irradiation using (I) SrFe₂O₄, (II) TiFe₂O₅, (III) Sr_0.7Ti_0.3Fe₂O_4.3 and (IV) Sr_0.4Ti_0.6Fe₂O_4.6 NPs (Experimental conditions: catalyst dose, 0.2 g/L for p-nitrophenol and pendimethalin, 0.4 g/L for martius yellow; pH, 3.0; irradiation time, 2 h and concentration 0.5 mg/L (p-nitrophenol and pendimethalin) and 0.05 mg/L (Martius yellow); Figure S4. Langmuir-Hinshelwood kinetic plots on photodegradation of nitroaromatic pollutants using (a) SrFe₂O₄, (b) TiFe₂O₅ and (c) Sr_0.7Ti_0.3Fe₂O_4.3 and (d) effect of catalyst dose dose. Experimental conditions: pH, 3.0; irradiation time, 2 h and concentration 0.5 mg/L (p-nitrophenol and pendimethalin and 0.05 mg/L (martius yellow)). Reference [35] is cited in the supplementary materials.

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