Fabrication of Green synthesized Lanthanum-Doped Bismuth Ferrite Perovskite type Nanocomposite for Photocatalytic Removal of Ibuprofen from Aqueous Solution

Fabrication of Green synthesized Lanthanum-Doped Bismuth Ferrite Perovskite type Nanocomposite for Photocatalytic Removal of Ibuprofen from Aqueous Solution | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article Fabrication of Green synthesized Lanthanum-Doped Bismuth Ferrite Perovskite type Nanocomposite for Photocatalytic Removal of Ibuprofen from Aqueous Solution Rasmirekha Pattanaik, Rishabh Kamal, Debapriya Pradhan, Suresh Kumar Dash This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-6543925/v1 This work is licensed under a CC BY 4.0 License Status: Under Review Version 1 posted 11 You are reading this latest preprint version Abstract Ibuprofen is a potential environmental toxin and carcinogen for freshwater ecosystems, posing significant risks to human health, particularly through its impact on kidney function. This research introduced a new type of bismuth ferrite perovskite material, modified with separable lanthanum, to explore how sunlight can be used to break down ibuprofen in water. The catalysts used in the study were created through green synthesis and co-precipitation methods, and their characteristics were analyzed using various techniques like X-ray diffractometry (XRD), Field Scanning emission microscopy (FE-SEM), X-ray photoelectron spectroscopy(XPS), UV-VIS absorption spectroscopy(UV-DRS) and Photoluminescence spectra(PL). The research explored the effect of photocatalysis on ibuprofen degradation. Pseudo-first-order kinetic model were used to assess the degradation rate of ibuprofen. The addition of 1% lanthanum to BiFeO 3 increased the material's surface area and pore capacity significantly, resulting increase in photocatalytic ibuprofen mineralization efficiency. The paper also provides a probable mechanism for how lanthanum doping effects the formation of BiFeO 3 nanoparticles and their photocatalytic activity based on experimental data. The catalytic properties of the bio-synthesized La-BFO nanoparticles were then assessed by their ability to degrade under various laboratory conditions. This demonstrates that the phytochemical from moringa oleifera provides an inexpensive and environmentally friendly approach for synthesizing catalytic nanoparticles that can break down highly toxic drugs. Moringa oleifera Lam Leaves Green synthesis La-BiFeO 3 Drugs Mechanism Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 Figure 9 1. Introduction Global pharmaceutical consumption has climbed 2.8 times during the last 15 years.. In 2015 [ 1 ], nations in the Organisation for Economic Cooperation and Development (OECD) projected their aggregate spending on prescription medications to be US $ 800 billion [ 2 ]. In 2013, the United States Food and Drug Administration (FDA) approved almost 100 new pharmaceutical chemicals or chemical entities for medical use. [ 3 ].By 2015, the worldwide pharmaceutical industry was worth $ 1.06 trillion, representing a 5.2% annual growth rate. Regionally, North America had the highest share at US $ 363.2 billion, followed by Europe at US $ 315.1 billion and Asia at US $ 281.3 billion [ 4 ]. As a result of increased pharmaceutical manufacturing and use, pharmaceutical levels in wastewater have grown significantly [ 5 ]. Persistent pharmaceutical compounds and personal care products (PPCPs) have been detected in a variety of water bodies, including wastewater treatment plant effluent, groundwater, and surface water sources. [ 6 ]. These compounds eventually infiltrate the natural environment, mostly through wastewater, posing substantial hazards due to their toxicity, ability to affect endocrine systems, and role in antibiotic resistance [ 7 ]. Ibuprofen (IBP), a popular nonsteroidal anti-inflammatory medicine (NSAID), is the third most regularly used medication to treat pain, fever, inflammation, and mild injuries [ 8 ]. With an annual global output of over 15,000 tonnes, roughly 70–80% of ibuprofen eaten is excreted by the body, either unaltered or as metabolic byproducts, eventually making its way into wastewater systems [ 9 ]. The presence of ibuprofen in both influent and effluent streams of wastewater treatment plants (WWTPs) has been observed [ 10 – 11 ], underlining the limits of existing treatment technology in completely eliminating this chemical before it reaches natural systems. This limitation emphasizes the critical need for more advanced and efficient treatment options. Among them, advanced oxidation processes (AOPs), notably those using heterogeneous photocatalysis, have shown tremendous promise. In degrading persistent organic pollutants, these techniques outperform traditional treatments by providing quicker response rates, higher efficiency, and more cost-effectiveness [ 12 ]. A newly developing class of nano-materials with a perovskite-like structure has sparked significant attention for a variety of applications, most notably photocatalytic degradation. Within the family of ABX 3 -type perovskite photocatalysts [ 13 ], bismuth-containing oxides, such as bismuth ferrite (BiFeO 3 ), have emerged as very promising third-generation photocatalysts capable of exploiting visible light.BiFeO 3 (BFO) is notable for its distorted rhombohedral perovskite structure, which makes it exceptionally efficient in the photodegradation of organic contaminants [ 14 ].BFO's attraction arises from numerous features, including its ability to absorb visible light due to a narrower bandgap, its noteworthy multiferroic properties at ambient temperature (25°C), and its exceptional chemical stability. [ 15 ]. These multiferroic features originate from the peculiar coexistence of ferroelectric and magnetic behaviors, which are related to the 6s 2 lone pair electrons of Bi 3+ ions and the partly filled 3d 5 shell of Fe 3+ ions [ 16 – 17 ]. This unique mixture promotes effective charge carrier separation, hence improving photocatalytic efficacy.BFO has previously demonstrated its efficacy in degrading a number of organic pollutants, including MB(methylene blue) [ 18 ], MO( methyl orange) [ 19 ], RhB(rhodamine B) [ 20 ], CR(congo red) [ 21 ], cefixime [ 22 ], oxalic acid [ 23 ], and norfloxacin [ 24 ], highlighting its promise as a diverse and efficient photocatalyst. Despite being regarded as a highly reactive and effective photocatalyst in visible light, pure BiFeO 3 has low photocatalytic activity in the degradation of organic pollutants [ 25 ]. This decreased efficiency is due to electron-hole recombination on the surface and within the material, a relatively low conduction band level in comparison to its redox potential and a finite surface area accessible for reactions [ 26 ]. Adding rare earth metals or transition elements to the BiFeO 3 structure can significantly improve its optical and photocatalytic characteristics. Similarly, heterostructures are a highly successful modification strategy that considerably improves the stability, dispersion, and recyclability of pure BiFeO 3 and its ability to photodegrade organic pollutants. The passage of electrons (e − ) and holes (h + ) across semiconductor materials in heterojunctions reduces charge carrier recombination, prolonging the lifespan of e − - h + couples [ 27 ]. Numerous investigations have demonstrated that adding rare earth metals to BiFeO₃ nanoparticles, such as cerium (Ce) [ 28 ], strontium (Sr) [ 29 ], gadolinium (Gd) [ 30 ], and yttrium (Y) [ 31 ], improves both their optical properties and photocatalytic activity [ 31 ], improves both their optical properties and photocatalytic activity. To enhance the purity of the material's phase, metal elements can be introduced into either the A or B sites of its structure. Research indicates that replacing La³⁺ and Er³⁺ at the A site of BiFeO₃ stabilises the perovskite phase, minimises Bi ion loss owing to vaporisation, and decreases oxygen vacancies [ 32 ]. A more environmentally friendly method for producing metal oxide nanoparticles, utilizing moringa oleifera, has been successfully employed to synthesize pure BiFeO 3 nanoparticles through a straightforward co-precipitation technique [ 33 ]. Incorporating rare earth metals into BiFeO 3 can improve its photocatalytic performance by leading to smaller particle sizes, increased surface area, and a narrower band gap. In photocatalysis, the dopant helps to reduce the recombination of electrons and holes generated by light by trapping the photoinduced electrons at favorable energy levels [ 34 ]. In this study, lanthanum was selected as the doping material. The substitution of Bi 3+ ions with lanthanum can lead to distortions and an expansion of the crystal lattice structure [ 35 ]. Furthermore, the research investigated the optical characteristics and photo-catalytic performance of both lanthanum doped and undoped BiFeO 3 synthesized using a green synthesis method. The primary goal of this study was to degrade significant amounts of ibuprofen using direct sunlight. The findings revealed that different concentrations of the lanthanum dopant influenced the photocatalytic activity, and the optimal doping level was determined. 2. Experimental study 2.1 Materials This study utilized high-purity Lanthanum nitrate hexahydrate (La(NO 3 ) 3 .6H 2 O),Bismuth nitrate Pentahydrate (Bi(NO 3 ) 3 .5H 2 O),Iron(III) nitrate nonahydrate (Fe(NO 3 ) 3 ).9H 2 O) salts, as well as moringa olefeira leaves. These chemicals were purchased from Sigma-Aldrich and Burkina Faso. Meanwhile, R&M Chemicals contributed 37% HCl and NaOH pellets. Ibuprofen was acquired at a pharmacy shop. Finally, distilled water (D.W.) was utilized throughout the study. 2.2 Preparation of lanthanum-doped BiFeO 3 nanoparticles 2.2.1 Preparation of a plant extract 30g of dried moringa oleifera leaves were soaked in 300 ml of heated deionized water (DI-H 2 O) and maintained at 50°C for approximately one hour and 45 minutes. After this, the solution was allowed to settle to ambient temperature before the leaves were removed by decanting the supernatant. The resulting extract was then filtered using filter paper and stored at 40°C for subsequent experiments. 2.2.2 Green synthesis of lanthanum doped BiFeO 3 Natural moringa plant extract (50 ml) was used as a solvent to dissolve 3 g of each precursor (La, Bi, and Fe). These precursors were dissolved in the plant extract at room temperature, without the use of heat or other chemicals, and the combination was covered with foil and allowed to react for 18 hours. It's worth noting that the combination of bismuth and iron created a suspension, since no precipitation was seen. Then the solution was then dried in an oven at 100 0 C, and the resultant powder was collected. The lanthanum-doped BiFeO 3 powder was then washed numerous times with distilled water. Finally, the powder was annealed in air at 500°C for 2 hours before being analyzed and used [ 36 ]. 2.3 Characterizations The nanocrystals were examined microstructurally with a field-emission scanning electron microscope (FE-SEM, Hitachi SU4300SE) and a high-resolution transmission electron microscope (HRTEM, JEOL JEM-ARM200FTH) with Selected-area electron diffraction (SAED) patterns. Their crystal structure and elemental content were determined using X-ray diffraction (XRD, Rigaku Ultima IV) and energy-dispersive X-ray spectroscopy (EDS), which were built into the FESEM devices. The chemical states of the elements were examined by X-ray photoelectron spectroscopy (XPS, ULVAC-PHI ESCA1700R) utilizing Al Kα radiation as the excitation source.A Shimadzu UV-2600i spectrometer with an integrating sphere was used to measure UV-visible diffuse reflectance spectra (DRS).A Hitachi F-7000 spectrometer was used to analyze steady state photoluminescence (PL) spectra at 532 nm excitation wavelength. Time resolved PL spectra were obtained using a single photon-counting system containing sub nanosecond pulsed diode laser (λ = 532 nm, picoQuant PDL 800-D).The system's instrument response function had a full width at half maximum (FWHM) of 25 ps. The decay data were fitted with a biexponential kinetic model to derive two distinct lifespan components. 2.4 Photocatalytic ibuprofen degradation The photocatalytic performance of La-BiFeO 3 nanocrystals was assessed by observing the photodegradation of ibuprofen in a simulated reaction. A typical process involved mixing 20 mL of a 20 ppm aqueous ibuprofen solution with La-BiFeO 3 in a volumetric flask. Before beginning the photocatalytic process, the system was left in the dark for 60 minutes to allow adsorption and desorption equilibrium to be established. The solution was then exposed to sunlight to aid in the photodegradation of ibuprofen. To follow the drop in ibuprofen concentration over time, 0.25 mL samples were removed from the reaction solution, centrifuged, and absorbance measured at λ = 220 nm [ 37 ]. The amount of drug adsorbed at equilibrium, denoted as q e (mg/g), and the percentage of ibuprofen removal were determined using the following equations. q e = \(\:\frac{{(\varvec{C}}_{0}-{\varvec{C}}_{\varvec{t}})\times\:\varvec{V}}{\varvec{m}}\) (1) Removal efficiency (%) = \(\:\frac{{(\varvec{C}}_{0}-{\varvec{C}}_{\varvec{t}})\times\:100}{{\varvec{C}}_{0}}\) (2) Where C 0 (mg/L) is the initial conc., C e (mg/L) is the conc. at eq. time (min),volume (l) is the volume of the ibuprofen solution and mass of the adsorbent (g). 2.5 Scavenger experiments To identify the principal reactive species involved in the photodegradation process, four different radical scavengers were added at 1 mM concentrations: ethylenediaminetetraacetic acid (EDTA), isopropanol (IPA), and benzoquinone (BQ) [ 38 ]. These compounds effectively capture photogenerated electrons, holes (h + ), hydroxyl radicals ( • OH), and superoxide radicals ( • O 2 − ) created during ibuprofen's photocatalytic breakdown. The typical experimental approach involved adding a consistent quantity (1mM) of each scavenger to the photocatalytic reaction mixture used to degrade ibuprofen. The ensuing ibuprofen concentration fluctuations were meticulously documented and compared to a control experiment in which no radical scavengers were utilized. 2.6 Reusability study To evaluate the reusability of La-BiFeO₃ nanocrystals in the photocatalytic degradation of ibuprofen, a four-cycle test was conducted under simulated sunlight conditions. In each cycle, 20 mL of a 20 ppm aqueous ibuprofen solution was mixed with the La-BiFeO₃ photocatalyst in a volumetric flask. The suspension was exposed to sunlight to initiate the photodegradation process for 90 minutes .After each cycle, the catalyst was recovered by centrifugation, thoroughly washed with distilled water, and dried before being reused in the subsequent cycle under identical experimental conditions. The photocatalytic efficiency of the reused La-BiFeO₃ nanocrystals was monitored to assess their stability and performance over the four consecutive degradation cycles. 3. Characterization 3.1 Crystallographic structure and morphology XRD (X-ray diffraction) pattern of BiFeO 3 and La-doped BiFeO 3 shown in Fig. 1 were produced using 30g of Moringa oleifera leaves using a green synthesis process, which was compared to that of the undoped sample. The results showed that both XRD patterns had comparable peaks, demonstrating the high purity of BiFeO 3 , regardless of lanthanum doping concentration. Figure 1 shows the XRD pattern of BiFeO₃ nanoparticles, which confirms a highly crystalline rhombohedral structure. The diffraction peaks at 2θ values of 22.5°, 32.1°, 39.6°, 46.2°, 51.9°, 57.4°, and 67.3° correspond to the (012), (110), (202), (014), (116), and (300) crystal planes of rhombohedral BiFeO₃, according to the JCPDS reference card No. 01-073-0548 [ 39 ]. The average crystallite size, even after doping, was determined to be 14.76 nm using the Debye-Scherrer formula. Increasing the quantity of La dopant resulted in a reduction in the strength of the diffraction peak corresponding to the [110] plane, shifting it towards lower 2θ values. This finding might be attributable to a fall in bismuth concentration followed by the incorporation of lanthanum ions [ 40 ].Furthermore, the loss of Bi 3+ ions by volatilization caused vacancies at the A site, which aided the doping process. The strength of the [110] peak varied, suggests that the particle size of the rhombohedral phase decreased as the La dopant concentration increased. However, the diminution and shift in the [110] crystalline peak showed a preferential crystallographic growth and orientation in that direction. Notably, the addition of La dopant to BiFeO 3 had no effect on the total crystallite size. To ensure the purity of the produced materials, EDX spectroscopy was used to examine the chemical composition of both the BiFeO 3 and La-doped BiFeO 3 nanoparticles. The EDX patterns shown in Fig. 2 (b-b1) demonstrated the excellent purity of the produced nanoparticles. FESEM images in Fig. 2 (a-a1) show that smaller cube like agglomeration of BiFeO 3 nanoparticles have a rhombohedral shape and higher particle sizes than undoped nanoparticles. The (1%) La-doped BiFeO 3 nanoparticles' smaller grain size was due to the densification of La 3+ , which took over the Bi 3+ sites. The addition of a modest quantity of lanthanum enhanced the sample's surface area due to the creation and dispersion of smaller particles, as seen by the FESEM analysis (Fig. 2 (a-a2)). The addition of 1% lanthanum to BiFeO 3 reduces particle size, resulting in a large surface area for active sites. The dopant's "grain growth inhibition" effect accounts for this. It will reduce particle size because dopants generally operate to pin grain borders, limiting grain boundary movement. The concentration of maximal dopant increases with the grain's surface to volume ratio and is greater for nanosized grains. Above a 1% lanthanum concentration, a new (dopant-rich) phase precipitates. Precipitation occurs at lower dopant concentrations, and as particle size rises, bigger crystals form. In theory, the surface area of the samples affects their photocatalytic activity [ 41 ]. As a result, it was expected that photocatalysts with smaller particle sizes would provide superior photocatalytic performance. Furthermore, the band gap energy of the samples will be influenced by photocatalysts of this particle size. Compositions of each element in the nanocomposites were confirmed from the EDAx spectrum shown in Fig. 2 a1-a3. The HRTEM picture of La-BiFeO 3 nanoparticles confirmed the cube-like crystallinity and lattice spacing of the produced sample in Fig. 3 a. Figure 3a1 shows that the interplanar spacing for the [110] plane of the sample calcined at 500°C was 0.28 nm, which is consistent with the XRD study results and Fig. 3 a2 shows SAED image of La-BiFeO 3 .The results indicate the creation of high purity La-BiFeO 3 nanoparticles using green synthesis. The production of BiFeO 3 nanoparticles might be established if the vibrational frequencies of chemical bonding in perovskite BiFeO 3 are identified. For example, in the 700-450cm − 1 range, vibration bands associated with metal and oxygen can be detected. The Ftir spectra of BiFeO 3 nanoparticles are presented in Fig. 3 . Octahedral FeO 6 groups with unique Fe-O stretching and bending vibration modes at 550 and 420 cm − 1 , respectively, were discovered in crystal lattices. According to the relevant study, the distinctive IR peaks of BiFeO 3 originate at higher frequencies for greater particle sizes. Furthermore, the stretching and bending of water molecules on the surface, as well as their absorption by OH, have been connected to IR bands at 3000 and 1480 cm − 1 , respectively. The band at 1070cm − 1 , on the other hand, might be caused by stretching vibrations of the nitrate ions created by HNO 3 during synthesis [ 42 ]. 3.2 Chemical States and Electronic Interaction The La-BiFeO₃ nanocrystals under study are a conventional metal-semiconductor heterostructure, combining a rare earth element from the lanthanide family (La) with the semiconductor BiFeO₃. This structure is known to improve charge-carrier separation during solar irradiation, which is an important component in increasing photocatalytic efficiency. X-ray photoelectron spectroscopy (XPS) was used to further understand the electrical interactions between La and BiFeO₃. This approach is useful in analysing the electronic structure and determining how the insertion of La affects charge transfer dynamics—an important feature for optimising the photocatalytic activity of nanocrystals. In Fig. 5 , the XPS spectra for La 3d, Bi 4f, Fe 2p, and O 1s show characteristic doublets corresponding to the chemical states of the lanthanide series element La and BiFeO 3 . The La 3d spectra of La-BiFeO 3 reveal four distinct peaks at 835.79, 839.55, 552.8, and 555.1 eV. The Bi 4f spectra display peak positions at 163.4 eV for Bi 4f 5/2 and 157.35 eV for Bi 4f 7/2. In the Fe 2p spectra, there is a prominent doublet (723.9 eV for Fe 2p1/2 and 712.11 eV for Fe 2p3/2) along with two satellite doublets at 732.3 and 719.3 eV. The O 1s spectra show two deconvoluted doublets, corresponding to lattice oxygen at 531.0 eV and surface oxygen due to chemical absorption at 528.2 eV, reflecting the crystal's spectral properties. The enhanced surface oxygen detected in the O 1s spectra is most likely due to the changed chemical environment caused by the La alteration process. X-ray photoelectron spectroscopy (XPS) indicates significant electronic interactions between La and BiFeO₃, essential for photodegradation applications. These interactions are expected to promote charge carrier separation and structural stability, hence increasing the photocatalytic efficacy of nanocrystals in environmental cleaning operations. 3.3 Optical Properties Figure 6 (a) shown the UV-DRS spectra of BiFeO 3 and (1%, 3%) La- doped BiFeO 3 . These spectra reveal that when 1% La-doped BiFeO 3 was compared to undoped and other percentage samples and absorption in the visible light region increased significantly that migrated to a higher wavelength. This is due to surface plasmon resonance (SPR) of La particles in the hetrostructure, which alters the optical properties of BiFeO 3 . The bandgap energy was determined using the Kubelka-Munk formula. $$\:\varvec{\alpha\:}\varvec{h}\varvec{\upsilon\:}=\varvec{A}{(\varvec{h}\varvec{\upsilon\:}-\mathbf{E}\mathbf{g})}^{2}$$ 1 Where α is the absorption coefficient, υ is the light frequency, Eg is the bandgap energy, and A is a constant. As shown in Fig. 6 (b), the bandgap energy (Eg) of BiFeO 3 and (1%, 3%) La-doped BiFeO 3 is 2.53eV, 2.04eV, and 2.20eV, respectively, suggesting a dramatic change in bandgap energy in the case of 1% La-doped BiFeO 3 , resulting in a red shift. This is owing to the energy band matching of BiFeO 3 and the SPR effect of the La particle. Figure 6 (c) displays the PL emission spectra of BiFeO 3 and 1% La-doped BiFeO 3 at room temperature (excitation wavelength 452 nm). The PL spectra of BFO exhibit a strong emission, implying a high electron-hole recombination rate, where as in 1% La-doped BiFeO 3 , the weak emission spectra indicate a sluggish rate of electron-hole recombination. 4. Photocatalytic activity Lanthanum-doped bismuth ferrite (La-BFO) was explored for its advanced application in the photocatalytic breakdown of ibuprofen (IBU), a common non-steroidal anti-inflammatory drug widely used as a pain reliever and fever reducer [ 43 ].IBU ranks as the third most consumed pharmaceutical and is frequently detected in various aquatic environments [ 44 ]. Research has indicated that IBU undergoes metabolic transformation in humans and animals, and its excreted metabolites, often more toxic than the original compound, find their way into rivers, lakes, oceans, groundwater, and other water sources. Initial photocatalytic experiments on IBU degradation utilized 0.30g of catalyst in a 40ppm IBU solution under simulated sunlight. Figure 7 a illustrates that the adsorption-desorption of IBU in darkness led to a consistent decrease in pollutant concentration (C) over time, which was quantified spectrophotometrically by monitoring IBU's primary aromatic absorption band at 221nm [ 45 ]. The plots of ln(C/C 0 ) versus time (t), where C 0 represents the IBU concentration after dark adsorption, exhibited a linear relationship. Prior studies have established that pH can significantly influence photocatalytic degradation. To examine the impact of pH on photoreactions, a consistent set of parameters was employed: 0.03 g of La-BFO in 250 mL of a 40ppm ibuprofen solution. The pH was adjusted using dilute hydrochloric acid (0.01 M) and sodium hydroxide (0.01 M) solutions. Ibuprofen has a pKa value of 5.2 and exists predominantly in its neutral form at pH values below its pKa [ 46 ]. Figure 7 b shows the photodegradation of ibuprofen at pH levels of 3.0, 5.0, 7.0, and 9.0. The photocatalytic reaction at pH 3.0 demonstrated the highest activity, with the characteristic band at 221 nm diminishing after 90 minutes, resulting in 89% degradation. Ibuprofen, being a weak acid, was most effectively removed under acidic conditions (pH 3). Acidic pharmaceutical compounds exist as neutral molecules at pH values below their pKa, allowing them to interact with the catalyst surface through non-electrostatic interactions, primarily involving hydrogen bonds. In this experiment, at pH 3 (lower than pKa), neutral ibuprofen molecules were adsorbed onto the catalyst surface via non-electrostatic interactions [ 46 ]. The removal rate declined with increasing pH, likely due to the deprotonation of surface-active sites, which hindered their interaction with ibuprofen and impeded the formation of agglomerates [ 47 – 48 ]. With a fixed initial IBU concentration of 40 ppm, the catalyst dose was varied between 0.03g and 0.06g. The reaction was evaluated after 90 minutes of exposure to simulated sunlight to assess the impact of catalyst dosage on degradation efficiency. Figure 7b1 depicts the influence of catalyst dose on the breakdown rate of ibuprofen. When the catalyst dose was below 0.04g, the IBU degradation rate increased as the dosage was reduced to 0.03g. The degradation rate of IBU remained relatively constant at a dose of 0.04g, not showing a significant improvement. Although increasing the catalyst dose can provide more active sites for IBU degradation, once the dosage exceeds an optimal level, it can hinder the mass transfer of hydrogen peroxide in the solution, leading to a decrease in the reaction rate. As the catalyst facilitated the generation of hydroxyl radicals through hydrogen peroxide, an increase in dose would initially lead to a rise in hydroxyl radical production [ 50 ]. However, at higher doses, these hydroxyl radicals may collide and quench each other, resulting in a reduced rate of IBU breakdown. Based on these observations, the optimal catalyst dose was determined to be 0.03g. The initial IBU concentration was varied from 10 to 40 ppm. Figure 7b2 illustrates the separation efficiency as a function of this initial concentration. The separation rate decreased as the concentration increased. Raising the concentration from 10 to 40 ppm led to stable froth formation. At a concentration of 40 ppm, both the undoped and doped samples achieved a maximum removal rate of approximately 88.89%. Beyond a critical value of 60 ppm, the removal rate diminished. This reduction can be attributed to several factors: (1) the formation of complexes with other ions present, (2) competition for available binding sites on the catalyst surface, (3) saturation of air bubbles in the system, and (4) a reduction in the size of the air bubbles [ 49 ]. The UV-Vis absorbance spectra of the IBP aqueous solution after irradiation with simulated solar light on the composites are shown in Fig. 7 c. A slight blue shift from 221 to 224 nm, potentially associated with deprotonation, was observed. However, the most significant degradation efficiency was achieved after 90 minutes of irradiation. Figure 7 d demonstrates that the photocatalytic degradation of IBU using both pristine BFO and La-BFO followed pseudo-first-order kinetics. The correlation coefficient (R 2 ) for degradation was 0.9008 and 0.9994 for BFO and La-BFO, respectively. The photocatalytic degradation efficiency of 1% La-BFO (89%) for IBU (40 ppm) surpassed that of the undoped catalyst and other doping percentages. 5. Possible phodegradtion mechanism Experiments to trap reactive radicals were also performed. Ethylenediaminetetraacetic acid (EDTA), benzoquinone (BQ), and isopropyl alcohol (IPA) were employed as scavengers to capture photogenerated holes (h + ), superoxide radicals (O 2 −• ), and hydroxyl radicals ( • OH), respectively. Figure 8 illustrates that the addition of BQ (0.5 mmol/L, 40 mL) did not significantly impact the degradation efficiency. However, the inclusion of EDTA and IPA at the same concentration and volume led to an approximate 50% reduction in degradation. This suggests that the photocatalytic process relies on both photogenerated holes and hydroxyl radicals, with hydroxyl radicals playing a more substantial role. As depicted in Fig. 8 b, repeated simulations of the model reaction using the recovered nanocatalyst yielded high conversion rates, indicating satisfactory catalytic stability. After four cycles of the model reaction using the recycled nanocatalyst, an average yield of 62% was achieved. These results underscore the stability and reusability of the nanoparticles. The consistently high conversion rates of the recycled catalyst suggest its potential for multiple reuses without a significant loss in its activity .Furthermore, the recovered catalyst was subjected to XRD analysis after washing drying and centrifugation ,as shown in Fig. 8 (c),interestingly revealed that the catalyst structure remain slightly unchanged even after four numerous reuse cycles. Collectively, these findings highlight the considerable potential of the synthesized nanoparticles as a stable and effective heterogeneous nanocatalyst under optimized reaction conditions. Overall, our findings demonstrate that the nanoparticles possess significant promise as a robust and efficient heterogeneous nanocatalyst when the reaction parameters are appropriately controlled. Upon illumination of the semiconductor (1% La-BFO) with light energy matching or exceeding its band gap, electrons are excited to the conduction band (CB), leaving behind holes in the valence band (VB) (Eq. 2). These photogenerated holes (h + ) can then react with water molecules to produce highly reactive hydroxyl radicals ( • OH) (Eq. 3), while the excited electrons reduce dissolved oxygen in the water, leading to the formation of superoxide anion radicals (O 2 •− ) (Eq. 4). These radicals subsequently participate in the partial or complete degradation of the ibuprofen (IBU) molecule. A comparison study described in a tabular form in table 1. The integration of La nanoparticles onto the BFO surface results in the formation of a heterojunction at the metal-semiconductor interface, characterized by a rectifying contact. Under thermal equilibrium, the Fermi energy levels of both materials align, causing electrons to transfer from the semiconductor to the metal (La work function, ϕLa = 2.85 eV), which is lower than that of the semiconductor (BiFeO 3 work function ≈ 4.7 eV). This rectifying contact, with a downward bending of the semiconductor's energy bands, facilitates the movement of electrons into the metal. Consequently, when the La-BFO composite is exposed to light, the photogenerated electrons tend to migrate towards the La nanoparticles. The metallic La acts as an efficient electron scavenger, thereby hindering the undesirable recombination of photogenerated electrons and holes (e − - h + ). Furthermore, La nanoparticles exhibit surface plasmon resonance (SPR) upon absorbing visible light, which can also contribute to the generation of superoxide anion radicals (O 2 •− ). During the photocatalytic degradation of ibuprofen, these superoxide anion radicals can initiate decarboxylation, leading to the formation of isobutyl acetophenone as an intermediate, which is further transformed into p-Isobutyl-phenol as the primary product. Additionally, the presence of hydroxyl radicals ( • OH) promotes hydroxylation reactions, resulting in the formation of 1-(4-isobutylphenyl) ethanol, which then undergoes demethylation to also yield p-Isobutylphenol. La-BiFeO 3 + hν →e − +h + (2) h + +H 2 O →OH.+H + (3) e − +O 2 →O 2 . − (4) SL.No. Catalyst Amount Light Source Time (min) %D Ref. 1 ZnO 1g/L UV 60 86.6 [ 51 ] 2 TiO 2 and ZnO 1mg UV/LED 90 99.99 [ 52 ] 3 Pd-TiO 2 /ZSM-5 0.17gL − 1 UVC irradiation 300 59.7 [ 53 ] 4 TiO 2 0.03 g mercury lamp (125 W) 5 100 [ 54 ] 5 Cu/Ag– BiVO4 - visible-light irradiation 300 89 and 96 [ 55 ] 6 La-BiFeO 3 0.03g Solar light 90 89 Current work 6. Conclusion Lanthanum-doped bismuth ferrite (La-BFO) was produced using an ecologically benign approach. The X-ray diffraction (XRD) patterns revealed the distinctive peaks associated with bismuth ferrite's rhombohedral crystal structure. The addition of lanthanum nanoparticles to the surface of BiFeO 3 reduced the absorbance of the La-BFO nanocomposites, implying a further reduction in bismuth ferrite. Photocatalytic assessments revealed that in alkaline settings, the La-BFO nanocomposites produced byproducts during the experiment's early phases. Lanthanum functions as an electron scavenger, reducing electron-hole recombination and promoting the creation of byproducts. Furthermore, the pH of the solution impacted ibuprofen (IBP) adsorption onto La-BFO, with neutral circumstances producing more intermediate compounds than alkaline and acidic conditions, respectively. Declarations Acknowledgment The authors are appreciative to the department of chemistry at ITER, Siksha 'O' Anusandhan (Deemed to Be University), Bhubaneswar for providing laboratory space for this work. We thank various research centers, including Kalinga Institute of Industrial Technology and National Institute of Technology Rourkela, for sharing their analytical techniques. Funding: No funding Author information: Authors and affiliations Department of Chemistry,ITER, Siksha ‘O’ Anusandhan (Deemed to be University) Bhubaneswar, Odisha 751030, India. Rasmirekha Pattanaik, Rishabh Kamal, Debapriya Pradhan, Suresh Kumar Dash Department of Chemistry, Centurion University of Technology and Management, Bhubaneswar, Odisha, 761211 , India. Debapriya Pradhan Authors’ contribution: Rasmirekha Pattanaik conducted the experiments, collected the data, prepared the manuscript, and handled the characterization work. Suresh Kumar Dash provided critical insights, developed the research concept, and guided the project to completion. Debapriya Pradhan and Rishabh Kamal were engaged in the analysis of the data. All authors contributed significantly throughout the course of the study. The final manuscript was read and approved by all contributors. Materials and Data availability All data generated or analyzed during this study are included within this article. Additional data can be made available upon request. Corresponding author Corresponds to Suresh kumar dash Clinical trial number : not applicable Ethics declarations Ethics approval and consent to participate Not applicable Consent for publication Not applicable Competing Interest The authors declare no known financial or personal conflicts of interest that could have influenced the outcomes of this research. References Laermann-Nguyen U, Backfisch M (2021d) Innovation crisis in the pharmaceutical industry? A survey. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-6543925","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":454171895,"identity":"e91bd5b7-bbeb-4a10-926f-52103be47ead","order_by":0,"name":"Rasmirekha Pattanaik","email":"","orcid":"","institution":"ITER, Siksha ’O’ Anusandhan (Deemed to be University)","correspondingAuthor":false,"prefix":"","firstName":"Rasmirekha","middleName":"","lastName":"Pattanaik","suffix":""},{"id":454171896,"identity":"a3af110e-be2e-4658-a221-be1ae130d8a5","order_by":1,"name":"Rishabh Kamal","email":"","orcid":"","institution":"ITER, Siksha ’O’ Anusandhan (Deemed to be University)","correspondingAuthor":false,"prefix":"","firstName":"Rishabh","middleName":"","lastName":"Kamal","suffix":""},{"id":454171897,"identity":"8cb584e7-7a90-4abf-a04e-e00b0c0daca0","order_by":2,"name":"Debapriya Pradhan","email":"","orcid":"","institution":"ITER, Siksha ’O’ Anusandhan (Deemed to be University)","correspondingAuthor":false,"prefix":"","firstName":"Debapriya","middleName":"","lastName":"Pradhan","suffix":""},{"id":454171898,"identity":"3125eb62-2bc4-4fc8-8051-8dc64264a447","order_by":3,"name":"Suresh Kumar Dash","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA2klEQVRIiWNgGAWjYLACxgZmBgYJ5gNwLrFa2BJI1sJjQJyb5GfkPnz4c4e1vPzsns8fPtQwyPM3MLc9wKfF4Ea6sTHvmXTDDXfObpOccYzBcMYBxna89hlIpLFJM7YdZtwgkbuNmYeNgXEDA2ObBH6HpbH//Nl22H7+jJzHn3n+MdgT1MJwI42NgbftcGLDjRwGad42hkSCWgzOPGMGqkxP3nAjzUxyZp9E8ozDhBzWnsb48Webte38GcmPP3z4ZmPb397+DL/D0ABQMTMp6kfBKBgFo2AUYAUApiNGycRt/y4AAAAASUVORK5CYII=","orcid":"","institution":"ITER, Siksha ’O’ Anusandhan (Deemed to be University)","correspondingAuthor":true,"prefix":"","firstName":"Suresh","middleName":"Kumar","lastName":"Dash","suffix":""}],"badges":[],"createdAt":"2025-04-28 05:08:11","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-6543925/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-6543925/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":82505698,"identity":"e5565177-d72e-4b09-8615-f56f7e5954d8","added_by":"auto","created_at":"2025-05-12 09:33:19","extension":"jpg","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":42231,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eXRD patterns of undoped and La-doped BiFeO\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e3\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003e nanoparticles; (a) undoped, (b) 1% and (c) 3% of La- doped BiFeO\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e3\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003e.\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"1.jpg","url":"https://assets-eu.researchsquare.com/files/rs-6543925/v1/8401c6bc6cc9fb639eee8b65.jpg"},{"id":82506923,"identity":"d370b64e-28ff-4bcf-a290-7da4de19e8be","added_by":"auto","created_at":"2025-05-12 09:49:19","extension":"jpg","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":110852,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eFE-SEM image and EDAX of undoped and La-doped BiFeO\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e3\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003e nanoparticles; (a-a1) undoped, (a2-a3) 1% of La- doped BiFeO\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e3\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003e.\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"2.jpg","url":"https://assets-eu.researchsquare.com/files/rs-6543925/v1/a9d7a5d807a0c2fa5ceabe32.jpg"},{"id":82505707,"identity":"0636b038-ca15-4eef-b937-3bb4c1342481","added_by":"auto","created_at":"2025-05-12 09:33:19","extension":"jpg","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":71232,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eHR-TEM and SAED image of (a-a2) 1% of La-doped BiFeO\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e3\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003e.\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"3.jpg","url":"https://assets-eu.researchsquare.com/files/rs-6543925/v1/b944d144663f624b76cf2207.jpg"},{"id":82505705,"identity":"dfa72829-5b30-4211-9542-b537c52d004b","added_by":"auto","created_at":"2025-05-12 09:33:19","extension":"jpg","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":30247,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eFTIR spectrm of undoped and La-doped BiFeO\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e3\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003e nanoparticles; (a) undoped, (b) 1% and (c) 3% of La- doped BiFeO\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e3\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003e.\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"4.jpg","url":"https://assets-eu.researchsquare.com/files/rs-6543925/v1/8286e8b4316b679e223da789.jpg"},{"id":82506926,"identity":"1b845b40-48d7-4044-91df-fdf51df8ad1e","added_by":"auto","created_at":"2025-05-12 09:49:19","extension":"jpg","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":79740,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eXPS spectra of La 3d,Bi 4f,Fe\u0026nbsp; 2p,O 1s spectra for La-doped BiFeO\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e3\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003e nanoparticles.\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"5.jpg","url":"https://assets-eu.researchsquare.com/files/rs-6543925/v1/a18b07ebfa594ac6238efdcb.jpg"},{"id":82505704,"identity":"df4ea021-52ea-4ae2-91e9-7d898df2ff16","added_by":"auto","created_at":"2025-05-12 09:33:19","extension":"jpg","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":58057,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eUV-DRS, Tauc plot and PL spectra of undoped and (1% and 3%) La-doped BiFeO\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e3\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003e nanoparticles; (a) UV-DRS (a1) Tauc plot (a2)PL spectra.\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"6.jpg","url":"https://assets-eu.researchsquare.com/files/rs-6543925/v1/dfefd61b408c160f9f11f2ee.jpg"},{"id":82505710,"identity":"d13334e5-2285-42db-8b7e-7df9a2c5c165","added_by":"auto","created_at":"2025-05-12 09:33:19","extension":"jpg","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":138458,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003ephotocatalytic influences of undoped and (1% and 3%) La-doped BiFeO\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e3\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003e nanoparticles; (a) Adsorption-Desorption, Different parameters(b)pH (b1)Dosage(b2)initial conc.(c)Uv-abs(d)kinetic plot.\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"7.jpg","url":"https://assets-eu.researchsquare.com/files/rs-6543925/v1/8d49bfd2062a0db30433add0.jpg"},{"id":82506536,"identity":"48565e9c-9032-4151-b210-a7bccc8b1d60","added_by":"auto","created_at":"2025-05-12 09:41:19","extension":"jpg","order_by":8,"title":"Figure 8","display":"","copyAsset":false,"role":"figure","size":43077,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003e(a) Scavenger test (a1) Recyclability test of 1% La-doped BiFeO\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e3\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003e nanoparticles.\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"8.jpg","url":"https://assets-eu.researchsquare.com/files/rs-6543925/v1/c8e357d65b9f19b509f30ad8.jpg"},{"id":82505709,"identity":"f885eeb4-efed-402f-8e9f-bf7b9d3a02d9","added_by":"auto","created_at":"2025-05-12 09:33:19","extension":"jpg","order_by":9,"title":"Figure 9","display":"","copyAsset":false,"role":"figure","size":29672,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eProposal mechanism of IBU photodegrdation\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"9.jpg","url":"https://assets-eu.researchsquare.com/files/rs-6543925/v1/e08c554205833133323e528b.jpg"},{"id":82507961,"identity":"94568088-851b-4a3b-ac67-9504d686afab","added_by":"auto","created_at":"2025-05-12 10:05:20","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":1995465,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-6543925/v1/f45c8a39-9ca0-4012-836f-577ee3287b01.pdf"},{"id":82506528,"identity":"6f615974-b7a1-4c7b-bcf6-ed83fe638c5c","added_by":"auto","created_at":"2025-05-12 09:41:19","extension":"jpg","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":50121,"visible":true,"origin":"","legend":"\u003cp\u003eGraphical abstract\u003c/p\u003e","description":"","filename":"Graphicalabstract.jpg","url":"https://assets-eu.researchsquare.com/files/rs-6543925/v1/3818f05b45bc2c40402e64f4.jpg"},{"id":82506924,"identity":"b3500937-9fa7-40cc-9f4d-75c47228d29f","added_by":"auto","created_at":"2025-05-12 09:49:19","extension":"jpg","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":80333,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eScheme 1 Synthesis procedure of La-BFO simple co-precipitation method\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"scheme1.jpg","url":"https://assets-eu.researchsquare.com/files/rs-6543925/v1/15d3f52b189499804035134e.jpg"},{"id":82507700,"identity":"1376e7bd-ad53-4c78-afdd-463ca7b432a0","added_by":"auto","created_at":"2025-05-12 09:57:19","extension":"jpg","order_by":3,"title":"","display":"","copyAsset":false,"role":"supplement","size":59014,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eScheme 2 Schematic energy band diagram of (1%) doped La-BFO hetero-structure.\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"scheme2.jpg","url":"https://assets-eu.researchsquare.com/files/rs-6543925/v1/8fa253fb26b9ebbf3fb2cb53.jpg"}],"financialInterests":"No competing interests reported.","formattedTitle":"Fabrication of Green synthesized Lanthanum-Doped Bismuth Ferrite Perovskite type Nanocomposite for Photocatalytic Removal of Ibuprofen from Aqueous Solution","fulltext":[{"header":"1. Introduction","content":"\u003cp\u003e Global pharmaceutical consumption has climbed 2.8 times during the last 15 years.. In 2015 [\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e], nations in the Organisation for Economic Cooperation and Development (OECD) projected their aggregate spending on prescription medications to be US\u003cspan\u003e$\u003c/span\u003e 800\u0026nbsp;billion [\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e]. In 2013, the United States Food and Drug Administration (FDA) approved almost 100 new pharmaceutical chemicals or chemical entities for medical use. [\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e].By 2015, the worldwide pharmaceutical industry was worth \u003cspan\u003e$\u003c/span\u003e1.06 trillion, representing a 5.2% annual growth rate. Regionally, North America had the highest share at US\u003cspan\u003e$\u003c/span\u003e 363.2\u0026nbsp;billion, followed by Europe at US\u003cspan\u003e$\u003c/span\u003e 315.1\u0026nbsp;billion and Asia at US\u003cspan\u003e$\u003c/span\u003e 281.3\u0026nbsp;billion [\u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e]. As a result of increased pharmaceutical manufacturing and use, pharmaceutical levels in wastewater have grown significantly [\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]. Persistent pharmaceutical compounds and personal care products (PPCPs) have been detected in a variety of water bodies, including wastewater treatment plant effluent, groundwater, and surface water sources. [\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e]. These compounds eventually infiltrate the natural environment, mostly through wastewater, posing substantial hazards due to their toxicity, ability to affect endocrine systems, and role in antibiotic resistance [\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eIbuprofen (IBP), a popular nonsteroidal anti-inflammatory medicine (NSAID), is the third most regularly used medication to treat pain, fever, inflammation, and mild injuries [\u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e]. With an annual global output of over 15,000 tonnes, roughly 70\u0026ndash;80% of ibuprofen eaten is excreted by the body, either unaltered or as metabolic byproducts, eventually making its way into wastewater systems [\u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e]. The presence of ibuprofen in both influent and effluent streams of wastewater treatment plants (WWTPs) has been observed [\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e], underlining the limits of existing treatment technology in completely eliminating this chemical before it reaches natural systems. This limitation emphasizes the critical need for more advanced and efficient treatment options. Among them, advanced oxidation processes (AOPs), notably those using heterogeneous photocatalysis, have shown tremendous promise. In degrading persistent organic pollutants, these techniques outperform traditional treatments by providing quicker response rates, higher efficiency, and more cost-effectiveness [\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eA newly developing class of nano-materials with a perovskite-like structure has sparked significant attention for a variety of applications, most notably photocatalytic degradation. Within the family of ABX\u003csub\u003e3\u003c/sub\u003e-type perovskite photocatalysts [\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e], bismuth-containing oxides, such as bismuth ferrite (BiFeO\u003csub\u003e3\u003c/sub\u003e), have emerged as very promising third-generation photocatalysts capable of exploiting visible light.BiFeO\u003csub\u003e3\u003c/sub\u003e (BFO) is notable for its distorted rhombohedral perovskite structure, which makes it exceptionally efficient in the photodegradation of organic contaminants [\u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e].BFO's attraction arises from numerous features, including its ability to absorb visible light due to a narrower bandgap, its noteworthy multiferroic properties at ambient temperature (25\u0026deg;C), and its exceptional chemical stability. [\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e]. These multiferroic features originate from the peculiar coexistence of ferroelectric and magnetic behaviors, which are related to the 6s\u003csup\u003e2\u003c/sup\u003e lone pair electrons of Bi\u003csup\u003e3+\u003c/sup\u003e ions and the partly filled 3d\u003csup\u003e5\u003c/sup\u003e shell of Fe\u003csup\u003e3+\u003c/sup\u003e ions [\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e]. This unique mixture promotes effective charge carrier separation, hence improving photocatalytic efficacy.BFO has previously demonstrated its efficacy in degrading a number of organic pollutants, including MB(methylene blue) [\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e], MO( methyl orange) [\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e], RhB(rhodamine B) [\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e], CR(congo red) [\u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e], cefixime [\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e], oxalic acid [\u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e], and norfloxacin [\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e], highlighting its promise as a diverse and efficient photocatalyst.\u003c/p\u003e \u003cp\u003eDespite being regarded as a highly reactive and effective photocatalyst in visible light, pure BiFeO\u003csub\u003e3\u003c/sub\u003e has low photocatalytic activity in the degradation of organic pollutants [\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e]. This decreased efficiency is due to electron-hole recombination on the surface and within the material, a relatively low conduction band level in comparison to its redox potential and a finite surface area accessible for reactions [\u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e]. Adding rare earth metals or transition elements to the BiFeO\u003csub\u003e3\u003c/sub\u003e structure can significantly improve its optical and photocatalytic characteristics. Similarly, heterostructures are a highly successful modification strategy that considerably improves the stability, dispersion, and recyclability of pure BiFeO\u003csub\u003e3\u003c/sub\u003e and its ability to photodegrade organic pollutants. The passage of electrons (e\u003csup\u003e\u0026minus;\u003c/sup\u003e) and holes (h\u003csup\u003e+\u003c/sup\u003e) across semiconductor materials in heterojunctions reduces charge carrier recombination, prolonging the lifespan of e\u003csup\u003e\u0026minus;\u003c/sup\u003e - h\u003csup\u003e+\u003c/sup\u003e couples [\u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e]. Numerous investigations have demonstrated that adding rare earth metals to BiFeO₃ nanoparticles, such as cerium (Ce) [\u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e], strontium (Sr) [\u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e], gadolinium (Gd) [\u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e], and yttrium (Y) [\u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e31\u003c/span\u003e], improves both their optical properties and photocatalytic activity [\u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e31\u003c/span\u003e], improves both their optical properties and photocatalytic activity.\u003c/p\u003e \u003cp\u003eTo enhance the purity of the material's phase, metal elements can be introduced into either the A or B sites of its structure. Research indicates that replacing La\u0026sup3;⁺ and Er\u0026sup3;⁺ at the A site of BiFeO₃ stabilises the perovskite phase, minimises Bi ion loss owing to vaporisation, and decreases oxygen vacancies [\u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e]. A more environmentally friendly method for producing metal oxide nanoparticles, utilizing moringa oleifera, has been successfully employed to synthesize pure BiFeO\u003csub\u003e3\u003c/sub\u003e nanoparticles through a straightforward co-precipitation technique [\u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e]. Incorporating rare earth metals into BiFeO\u003csub\u003e3\u003c/sub\u003e can improve its photocatalytic performance by leading to smaller particle sizes, increased surface area, and a narrower band gap. In photocatalysis, the dopant helps to reduce the recombination of electrons and holes generated by light by trapping the photoinduced electrons at favorable energy levels [\u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e]. In this study, lanthanum was selected as the doping material. The substitution of Bi\u003csup\u003e3+\u003c/sup\u003e ions with lanthanum can lead to distortions and an expansion of the crystal lattice structure [\u003cspan citationid=\"CR35\" class=\"CitationRef\"\u003e35\u003c/span\u003e]. Furthermore, the research investigated the optical characteristics and photo-catalytic performance of both lanthanum doped and undoped BiFeO\u003csub\u003e3\u003c/sub\u003e synthesized using a green synthesis method. The primary goal of this study was to degrade significant amounts of ibuprofen using direct sunlight. The findings revealed that different concentrations of the lanthanum dopant influenced the photocatalytic activity, and the optimal doping level was determined.\u003c/p\u003e"},{"header":"2. Experimental study","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003e2.1 Materials\u003c/h2\u003e \u003cp\u003eThis study utilized high-purity Lanthanum nitrate hexahydrate (La(NO\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e3\u003c/sub\u003e.6H\u003csub\u003e2\u003c/sub\u003eO),Bismuth nitrate Pentahydrate (Bi(NO\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e3\u003c/sub\u003e.5H\u003csub\u003e2\u003c/sub\u003eO),Iron(III) nitrate nonahydrate (Fe(NO\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e3\u003c/sub\u003e).9H\u003csub\u003e2\u003c/sub\u003eO) salts, as well as moringa olefeira leaves. These chemicals were purchased from Sigma-Aldrich and Burkina Faso. Meanwhile, R\u0026amp;M Chemicals contributed 37% HCl and NaOH pellets.\u003c/p\u003e \u003cp\u003eIbuprofen was acquired at a pharmacy shop. Finally, distilled water (D.W.) was utilized throughout the study.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec4\" class=\"Section2\"\u003e \u003ch2\u003e2.2 Preparation of lanthanum-doped BiFeO\u003csub\u003e3\u003c/sub\u003e nanoparticles\u003c/h2\u003e \u003cdiv id=\"Sec5\" class=\"Section3\"\u003e \u003ch2\u003e2.2.1 Preparation of a plant extract\u003c/h2\u003e \u003cp\u003e30g of dried moringa oleifera leaves were soaked in 300 ml of heated deionized water (DI-H\u003csub\u003e2\u003c/sub\u003eO) and maintained at 50\u0026deg;C for approximately one hour and 45 minutes. After this, the solution was allowed to settle to ambient temperature before the leaves were removed by decanting the supernatant. The resulting extract was then filtered using filter paper and stored at 40\u0026deg;C for subsequent experiments.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec6\" class=\"Section3\"\u003e \u003ch2\u003e2.2.2 Green synthesis of lanthanum doped BiFeO\u003csub\u003e3\u003c/sub\u003e\u003c/h2\u003e \u003cp\u003eNatural moringa plant extract (50 ml) was used as a solvent to dissolve 3 g of each precursor (La, Bi, and Fe). These precursors were dissolved in the plant extract at room temperature, without the use of heat or other chemicals, and the combination was covered with foil and allowed to react for 18 hours. It's worth noting that the combination of bismuth and iron created a suspension, since no precipitation was seen. Then the solution was then dried in an oven at 100\u003csup\u003e0\u003c/sup\u003eC, and the resultant powder was collected. The lanthanum-doped BiFeO\u003csub\u003e3\u003c/sub\u003e powder was then washed numerous times with distilled water. Finally, the powder was annealed in air at 500\u0026deg;C for 2 hours before being analyzed and used [\u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e36\u003c/span\u003e].\u003c/p\u003e \u003c/div\u003e \u003c/div\u003e \u003cdiv id=\"Sec7\" class=\"Section2\"\u003e \u003ch2\u003e2.3 Characterizations\u003c/h2\u003e \u003cp\u003eThe nanocrystals were examined microstructurally with a field-emission scanning electron microscope (FE-SEM, Hitachi SU4300SE) and a high-resolution transmission electron microscope (HRTEM, JEOL JEM-ARM200FTH) with Selected-area electron diffraction (SAED) patterns. Their crystal structure and elemental content were determined using X-ray diffraction (XRD, Rigaku Ultima IV) and energy-dispersive X-ray spectroscopy (EDS), which were built into the FESEM devices. The chemical states of the elements were examined by X-ray photoelectron spectroscopy (XPS, ULVAC-PHI ESCA1700R) utilizing Al Kα radiation as the excitation source.A Shimadzu UV-2600i spectrometer with an integrating sphere was used to measure UV-visible diffuse reflectance spectra (DRS).A Hitachi F-7000 spectrometer was used to analyze steady state photoluminescence (PL) spectra at 532 nm excitation wavelength. Time resolved PL spectra were obtained using a single photon-counting system containing sub nanosecond pulsed diode laser (λ\u0026thinsp;=\u0026thinsp;532 nm, picoQuant PDL 800-D).The system's instrument response function had a full width at half maximum (FWHM) of 25 ps. The decay data were fitted with a biexponential kinetic model to derive two distinct lifespan components.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec8\" class=\"Section2\"\u003e \u003ch2\u003e2.4 Photocatalytic ibuprofen degradation\u003c/h2\u003e \u003cp\u003eThe photocatalytic performance of La-BiFeO\u003csub\u003e3\u003c/sub\u003e nanocrystals was assessed by observing the photodegradation of ibuprofen in a simulated reaction. A typical process involved mixing 20 mL of a 20 ppm aqueous ibuprofen solution with La-BiFeO\u003csub\u003e3\u003c/sub\u003e in a volumetric flask. Before beginning the photocatalytic process, the system was left in the dark for 60 minutes to allow adsorption and desorption equilibrium to be established. The solution was then exposed to sunlight to aid in the photodegradation of ibuprofen. To follow the drop in ibuprofen concentration over time, 0.25 mL samples were removed from the reaction solution, centrifuged, and absorbance measured at λ\u0026thinsp;=\u0026thinsp;220 nm [\u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e37\u003c/span\u003e]. The amount of drug adsorbed at equilibrium, denoted as q\u003csub\u003ee\u003c/sub\u003e (mg/g), and the percentage of ibuprofen removal were determined using the following equations.\u003c/p\u003e \u003cp\u003eq\u003csub\u003ee\u003c/sub\u003e \u003cb\u003e=\u003c/b\u003e \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:\\frac{{(\\varvec{C}}_{0}-{\\varvec{C}}_{\\varvec{t}})\\times\\:\\varvec{V}}{\\varvec{m}}\\)\u003c/span\u003e\u003c/span\u003e \u003cb\u003e(1)\u003c/b\u003e\u003c/p\u003e \u003cp\u003eRemoval efficiency (%) \u003cb\u003e=\u003c/b\u003e \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:\\frac{{(\\varvec{C}}_{0}-{\\varvec{C}}_{\\varvec{t}})\\times\\:100}{{\\varvec{C}}_{0}}\\)\u003c/span\u003e\u003c/span\u003e \u003cb\u003e(2)\u003c/b\u003e\u003c/p\u003e \u003cp\u003eWhere C\u003csub\u003e0\u003c/sub\u003e (mg/L) is the initial conc., C\u003csub\u003ee\u003c/sub\u003e (mg/L) is the conc. at eq.\u0026nbsp;time (min),volume (l) is the volume of the ibuprofen solution and mass of the adsorbent (g).\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec9\" class=\"Section2\"\u003e \u003ch2\u003e2.5 Scavenger experiments\u003c/h2\u003e \u003cp\u003eTo identify the principal reactive species involved in the photodegradation process, four different radical scavengers were added at 1 mM concentrations: ethylenediaminetetraacetic acid (EDTA), isopropanol (IPA), and benzoquinone (BQ) [\u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e38\u003c/span\u003e]. These compounds effectively capture photogenerated electrons, holes (h\u003csup\u003e+\u003c/sup\u003e), hydroxyl radicals (\u003csup\u003e\u0026bull;\u003c/sup\u003eOH), and superoxide radicals (\u003csup\u003e\u0026bull;\u003c/sup\u003eO\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e) created during ibuprofen's photocatalytic breakdown. The typical experimental approach involved adding a consistent quantity (1mM) of each scavenger to the photocatalytic reaction mixture used to degrade ibuprofen. The ensuing ibuprofen concentration fluctuations were meticulously documented and compared to a control experiment in which no radical scavengers were utilized.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec10\" class=\"Section2\"\u003e \u003ch2\u003e2.6 Reusability study\u003c/h2\u003e \u003cp\u003eTo evaluate the reusability of La-BiFeO₃ nanocrystals in the photocatalytic degradation of ibuprofen, a four-cycle test was conducted under simulated sunlight conditions. In each cycle, 20 mL of a 20 ppm aqueous ibuprofen solution was mixed with the La-BiFeO₃ photocatalyst in a volumetric flask. The suspension was exposed to sunlight to initiate the photodegradation process for 90 minutes .After each cycle, the catalyst was recovered by centrifugation, thoroughly washed with distilled water, and dried before being reused in the subsequent cycle under identical experimental conditions. The photocatalytic efficiency of the reused La-BiFeO₃ nanocrystals was monitored to assess their stability and performance over the four consecutive degradation cycles.\u003c/p\u003e \u003c/div\u003e"},{"header":"3. Characterization","content":"\u003cdiv id=\"Sec12\" class=\"Section2\"\u003e \u003ch2\u003e3.1 Crystallographic structure and morphology\u003c/h2\u003e \u003cp\u003eXRD (X-ray diffraction) pattern of BiFeO\u003csub\u003e3\u003c/sub\u003e and La-doped BiFeO\u003csub\u003e3\u003c/sub\u003e shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e were produced using 30g of Moringa oleifera leaves using a green synthesis process, which was compared to that of the undoped sample. The results showed that both XRD patterns had comparable peaks, demonstrating the high purity of BiFeO\u003csub\u003e3\u003c/sub\u003e, regardless of lanthanum doping concentration. Figure\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e shows the XRD pattern of BiFeO₃ nanoparticles, which confirms a highly crystalline rhombohedral structure. The diffraction peaks at 2θ values of 22.5\u0026deg;, 32.1\u0026deg;, 39.6\u0026deg;, 46.2\u0026deg;, 51.9\u0026deg;, 57.4\u0026deg;, and 67.3\u0026deg; correspond to the (012), (110), (202), (014), (116), and (300) crystal planes of rhombohedral BiFeO₃, according to the JCPDS reference card No. 01-073-0548 [\u003cspan citationid=\"CR39\" class=\"CitationRef\"\u003e39\u003c/span\u003e]. The average crystallite size, even after doping, was determined to be 14.76 nm using the Debye-Scherrer formula. Increasing the quantity of La dopant resulted in a reduction in the strength of the diffraction peak corresponding to the [110] plane, shifting it towards lower 2θ values. This finding might be attributable to a fall in bismuth concentration followed by the incorporation of lanthanum ions [\u003cspan citationid=\"CR40\" class=\"CitationRef\"\u003e40\u003c/span\u003e].Furthermore, the loss of Bi\u003csup\u003e3+\u003c/sup\u003e ions by volatilization caused vacancies at the A site, which aided the doping process. The strength of the [110] peak varied, suggests that the particle size of the rhombohedral phase decreased as the La dopant concentration increased. However, the diminution and shift in the [110] crystalline peak showed a preferential crystallographic growth and orientation in that direction. Notably, the addition of La dopant to BiFeO\u003csub\u003e3\u003c/sub\u003e had no effect on the total crystallite size. To ensure the purity of the produced materials, EDX spectroscopy was used to examine the chemical composition of both the BiFeO\u003csub\u003e3\u003c/sub\u003e and La-doped BiFeO\u003csub\u003e3\u003c/sub\u003e nanoparticles. The EDX patterns shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e(b-b1) demonstrated the excellent purity of the produced nanoparticles.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eFESEM images in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e(a-a1) show that smaller cube like agglomeration of BiFeO\u003csub\u003e3\u003c/sub\u003e nanoparticles have a rhombohedral shape and higher particle sizes than undoped nanoparticles. The (1%) La-doped BiFeO\u003csub\u003e3\u003c/sub\u003e nanoparticles' smaller grain size was due to the densification of La\u003csup\u003e3+\u003c/sup\u003e, which took over the Bi\u003csup\u003e3+\u003c/sup\u003e sites. The addition of a modest quantity of lanthanum enhanced the sample's surface area due to the creation and dispersion of smaller particles, as seen by the FESEM analysis (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e(a-a2)). The addition of 1% lanthanum to BiFeO\u003csub\u003e3\u003c/sub\u003e reduces particle size, resulting in a large surface area for active sites. The dopant's \"grain growth inhibition\" effect accounts for this. It will reduce particle size because dopants generally operate to pin grain borders, limiting grain boundary movement. The concentration of maximal dopant increases with the grain's surface to volume ratio and is greater for nanosized grains. Above a 1% lanthanum concentration, a new (dopant-rich) phase precipitates. Precipitation occurs at lower dopant concentrations, and as particle size rises, bigger crystals form. In theory, the surface area of the samples affects their photocatalytic activity [\u003cspan citationid=\"CR41\" class=\"CitationRef\"\u003e41\u003c/span\u003e]. As a result, it was expected that photocatalysts with smaller particle sizes would provide superior photocatalytic performance. Furthermore, the band gap energy of the samples will be influenced by photocatalysts of this particle size. Compositions of each element in the nanocomposites were confirmed from the EDAx spectrum shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ea1-a3.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe HRTEM picture of La-BiFeO\u003csub\u003e3\u003c/sub\u003e nanoparticles confirmed the cube-like crystallinity and lattice spacing of the produced sample in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ea. Figure\u0026nbsp;3a1 shows that the interplanar spacing for the [110] plane of the sample calcined at 500\u0026deg;C was 0.28 nm, which is consistent with the XRD study results and Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ea2 shows SAED image of La-BiFeO\u003csub\u003e3\u003c/sub\u003e.The results indicate the creation of high purity La-BiFeO\u003csub\u003e3\u003c/sub\u003e nanoparticles using green synthesis.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe production of BiFeO\u003csub\u003e3\u003c/sub\u003e nanoparticles might be established if the vibrational frequencies of chemical bonding in perovskite BiFeO\u003csub\u003e3\u003c/sub\u003e are identified. For example, in the 700-450cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e range, vibration bands associated with metal and oxygen can be detected. The Ftir spectra of BiFeO\u003csub\u003e3\u003c/sub\u003e nanoparticles are presented in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e. Octahedral FeO\u003csub\u003e6\u003c/sub\u003e groups with unique Fe-O stretching and bending vibration modes at 550 and 420 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, respectively, were discovered in crystal lattices. According to the relevant study, the distinctive IR peaks of BiFeO\u003csub\u003e3\u003c/sub\u003e originate at higher frequencies for greater particle sizes. Furthermore, the stretching and bending of water molecules on the surface, as well as their absorption by OH, have been connected to IR bands at 3000 and 1480 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, respectively. The band at 1070cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, on the other hand, might be caused by stretching vibrations of the nitrate ions created by HNO\u003csub\u003e3\u003c/sub\u003e during synthesis [\u003cspan citationid=\"CR42\" class=\"CitationRef\"\u003e42\u003c/span\u003e].\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec13\" class=\"Section2\"\u003e \u003ch2\u003e3.2 Chemical States and Electronic Interaction\u003c/h2\u003e \u003cp\u003eThe La-BiFeO₃ nanocrystals under study are a conventional metal-semiconductor heterostructure, combining a rare earth element from the lanthanide family (La) with the semiconductor BiFeO₃. This structure is known to improve charge-carrier separation during solar irradiation, which is an important component in increasing photocatalytic efficiency. X-ray photoelectron spectroscopy (XPS) was used to further understand the electrical interactions between La and BiFeO₃. This approach is useful in analysing the electronic structure and determining how the insertion of La affects charge transfer dynamics\u0026mdash;an important feature for optimising the photocatalytic activity of nanocrystals.\u003c/p\u003e \u003cp\u003eIn Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e, the XPS spectra for La 3d, Bi 4f, Fe 2p, and O 1s show characteristic doublets corresponding to the chemical states of the lanthanide series element La and BiFeO\u003csub\u003e3\u003c/sub\u003e. The La 3d spectra of La-BiFeO\u003csub\u003e3\u003c/sub\u003e reveal four distinct peaks at 835.79, 839.55, 552.8, and 555.1 eV. The Bi 4f spectra display peak positions at 163.4 eV for Bi 4f 5/2 and 157.35 eV for Bi 4f 7/2. In the Fe 2p spectra, there is a prominent doublet (723.9 eV for Fe 2p1/2 and 712.11 eV for Fe 2p3/2) along with two satellite doublets at 732.3 and 719.3 eV. The O 1s spectra show two deconvoluted doublets, corresponding to lattice oxygen at 531.0 eV and surface oxygen due to chemical absorption at 528.2 eV, reflecting the crystal's spectral properties. The enhanced surface oxygen detected in the O 1s spectra is most likely due to the changed chemical environment caused by the La alteration process. X-ray photoelectron spectroscopy (XPS) indicates significant electronic interactions between La and BiFeO₃, essential for photodegradation applications. These interactions are expected to promote charge carrier separation and structural stability, hence increasing the photocatalytic efficacy of nanocrystals in environmental cleaning operations.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec14\" class=\"Section2\"\u003e \u003ch2\u003e3.3 Optical Properties\u003c/h2\u003e \u003cp\u003eFigure \u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003e(a) shown the UV-DRS spectra of BiFeO\u003csub\u003e3\u003c/sub\u003e and (1%, 3%) La- doped BiFeO\u003csub\u003e3\u003c/sub\u003e. These spectra reveal that when 1% La-doped BiFeO\u003csub\u003e3\u003c/sub\u003e was compared to undoped and other percentage samples and absorption in the visible light region increased significantly that migrated to a higher wavelength. This is due to surface plasmon resonance (SPR) of La particles in the hetrostructure, which alters the optical properties of BiFeO\u003csub\u003e3\u003c/sub\u003e. The bandgap energy was determined using the Kubelka-Munk formula.\u003cdiv id=\"Equ1\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equ1\" name=\"EquationSource\"\u003e\n$$\\:\\varvec{\\alpha\\:}\\varvec{h}\\varvec{\\upsilon\\:}=\\varvec{A}{(\\varvec{h}\\varvec{\\upsilon\\:}-\\mathbf{E}\\mathbf{g})}^{2}$$\u003c/div\u003e\u003cdiv class=\"EquationNumber\"\u003e1\u003c/div\u003e\u003c/div\u003e\u003c/p\u003e \u003cp\u003eWhere α is the absorption coefficient, υ is the light frequency, Eg is the bandgap energy, and A is a constant. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003e(b), the bandgap energy (Eg) of BiFeO\u003csub\u003e3\u003c/sub\u003e and (1%, 3%) La-doped BiFeO\u003csub\u003e3\u003c/sub\u003e is 2.53eV, 2.04eV, and 2.20eV, respectively, suggesting a dramatic change in bandgap energy in the case of 1% La-doped BiFeO\u003csub\u003e3\u003c/sub\u003e, resulting in a red shift. This is owing to the energy band matching of BiFeO\u003csub\u003e3\u003c/sub\u003e and the SPR effect of the La particle.\u003c/p\u003e \u003cp\u003eFigure \u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003e(c) displays the PL emission spectra of BiFeO\u003csub\u003e3\u003c/sub\u003e and 1% La-doped BiFeO\u003csub\u003e3\u003c/sub\u003e at room temperature (excitation wavelength 452 nm). The PL spectra of BFO exhibit a strong emission, implying a high electron-hole recombination rate, where as in 1% La-doped BiFeO\u003csub\u003e3\u003c/sub\u003e, the weak emission spectra indicate a sluggish rate of electron-hole recombination.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e"},{"header":"4. Photocatalytic activity","content":"\u003cp\u003eLanthanum-doped bismuth ferrite (La-BFO) was explored for its advanced application in the photocatalytic breakdown of ibuprofen (IBU), a common non-steroidal anti-inflammatory drug widely used as a pain reliever and fever reducer [\u003cspan citationid=\"CR43\" class=\"CitationRef\"\u003e43\u003c/span\u003e].IBU ranks as the third most consumed pharmaceutical and is frequently detected in various aquatic environments [\u003cspan citationid=\"CR44\" class=\"CitationRef\"\u003e44\u003c/span\u003e]. Research has indicated that IBU undergoes metabolic transformation in humans and animals, and its excreted metabolites, often more toxic than the original compound, find their way into rivers, lakes, oceans, groundwater, and other water sources. Initial photocatalytic experiments on IBU degradation utilized 0.30g of catalyst in a 40ppm IBU solution under simulated sunlight. Figure\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003ea illustrates that the adsorption-desorption of IBU in darkness led to a consistent decrease in pollutant concentration (C) over time, which was quantified spectrophotometrically by monitoring IBU's primary aromatic absorption band at 221nm [\u003cspan citationid=\"CR45\" class=\"CitationRef\"\u003e45\u003c/span\u003e]. The plots of ln(C/C\u003csub\u003e0\u003c/sub\u003e) versus time (t), where C\u003csub\u003e0\u003c/sub\u003e represents the IBU concentration after dark adsorption, exhibited a linear relationship.\u003c/p\u003e \u003cp\u003ePrior studies have established that pH can significantly influence photocatalytic degradation. To examine the impact of pH on photoreactions, a consistent set of parameters was employed: 0.03 g of La-BFO in 250 mL of a 40ppm ibuprofen solution. The pH was adjusted using dilute hydrochloric acid (0.01 M) and sodium hydroxide (0.01 M) solutions. Ibuprofen has a pKa value of 5.2 and exists predominantly in its neutral form at pH values below its pKa [\u003cspan citationid=\"CR46\" class=\"CitationRef\"\u003e46\u003c/span\u003e]. Figure\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003eb shows the photodegradation of ibuprofen at pH levels of 3.0, 5.0, 7.0, and 9.0. The photocatalytic reaction at pH 3.0 demonstrated the highest activity, with the characteristic band at 221 nm diminishing after 90 minutes, resulting in 89% degradation. Ibuprofen, being a weak acid, was most effectively removed under acidic conditions (pH 3). Acidic pharmaceutical compounds exist as neutral molecules at pH values below their pKa, allowing them to interact with the catalyst surface through non-electrostatic interactions, primarily involving hydrogen bonds. In this experiment, at pH 3 (lower than pKa), neutral ibuprofen molecules were adsorbed onto the catalyst surface via non-electrostatic interactions [\u003cspan citationid=\"CR46\" class=\"CitationRef\"\u003e46\u003c/span\u003e]. The removal rate declined with increasing pH, likely due to the deprotonation of surface-active sites, which hindered their interaction with ibuprofen and impeded the formation of agglomerates [\u003cspan citationid=\"CR47\" class=\"CitationRef\"\u003e47\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR48\" class=\"CitationRef\"\u003e48\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eWith a fixed initial IBU concentration of 40 ppm, the catalyst dose was varied between 0.03g and 0.06g. The reaction was evaluated after 90 minutes of exposure to simulated sunlight to assess the impact of catalyst dosage on degradation efficiency. Figure\u0026nbsp;7b1 depicts the influence of catalyst dose on the breakdown rate of ibuprofen. When the catalyst dose was below 0.04g, the IBU degradation rate increased as the dosage was reduced to 0.03g. The degradation rate of IBU remained relatively constant at a dose of 0.04g, not showing a significant improvement. Although increasing the catalyst dose can provide more active sites for IBU degradation, once the dosage exceeds an optimal level, it can hinder the mass transfer of hydrogen peroxide in the solution, leading to a decrease in the reaction rate. As the catalyst facilitated the generation of hydroxyl radicals through hydrogen peroxide, an increase in dose would initially lead to a rise in hydroxyl radical production [\u003cspan citationid=\"CR50\" class=\"CitationRef\"\u003e50\u003c/span\u003e]. However, at higher doses, these hydroxyl radicals may collide and quench each other, resulting in a reduced rate of IBU breakdown. Based on these observations, the optimal catalyst dose was determined to be 0.03g.\u003c/p\u003e \u003cp\u003eThe initial IBU concentration was varied from 10 to 40 ppm. Figure\u0026nbsp;7b2 illustrates the separation efficiency as a function of this initial concentration. The separation rate decreased as the concentration increased. Raising the concentration from 10 to 40 ppm led to stable froth formation. At a concentration of 40 ppm, both the undoped and doped samples achieved a maximum removal rate of approximately 88.89%. Beyond a critical value of 60 ppm, the removal rate diminished. This reduction can be attributed to several factors: (1) the formation of complexes with other ions present, (2) competition for available binding sites on the catalyst surface, (3) saturation of air bubbles in the system, and (4) a reduction in the size of the air bubbles [\u003cspan citationid=\"CR49\" class=\"CitationRef\"\u003e49\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eThe UV-Vis absorbance spectra of the IBP aqueous solution after irradiation with simulated solar light on the composites are shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003ec. A slight blue shift from 221 to 224 nm, potentially associated with deprotonation, was observed. However, the most significant degradation efficiency was achieved after 90 minutes of irradiation. Figure\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003ed demonstrates that the photocatalytic degradation of IBU using both pristine BFO and La-BFO followed pseudo-first-order kinetics. The correlation coefficient (R\u003csup\u003e2\u003c/sup\u003e) for degradation was 0.9008 and 0.9994 for BFO and La-BFO, respectively. The photocatalytic degradation efficiency of 1% La-BFO (89%) for IBU (40 ppm) surpassed that of the undoped catalyst and other doping percentages.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e"},{"header":"5. Possible phodegradtion mechanism","content":"\u003cp\u003eExperiments to trap reactive radicals were also performed. Ethylenediaminetetraacetic acid (EDTA), benzoquinone (BQ), and isopropyl alcohol (IPA) were employed as scavengers to capture photogenerated holes (h\u003csup\u003e+\u003c/sup\u003e), superoxide radicals (O\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e\u0026minus;\u0026bull;\u003c/sup\u003e), and hydroxyl radicals (\u003csup\u003e\u0026bull;\u003c/sup\u003eOH), respectively. Figure\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e8\u003c/span\u003e illustrates that the addition of BQ (0.5 mmol/L, 40 mL) did not significantly impact the degradation efficiency. However, the inclusion of EDTA and IPA at the same concentration and volume led to an approximate 50% reduction in degradation. This suggests that the photocatalytic process relies on both photogenerated holes and hydroxyl radicals, with hydroxyl radicals playing a more substantial role.\u003c/p\u003e \u003cp\u003eAs depicted in Fig.\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e8\u003c/span\u003eb, repeated simulations of the model reaction using the recovered nanocatalyst yielded high conversion rates, indicating satisfactory catalytic stability. After four cycles of the model reaction using the recycled nanocatalyst, an average yield of 62% was achieved. These results underscore the stability and reusability of the nanoparticles. The consistently high conversion rates of the recycled catalyst suggest its potential for multiple reuses without a significant loss in its activity .Furthermore, the recovered catalyst was subjected to XRD analysis after washing drying and centrifugation ,as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e8\u003c/span\u003e(c),interestingly revealed that the catalyst structure remain slightly unchanged even after four numerous reuse cycles. Collectively, these findings highlight the considerable potential of the synthesized nanoparticles as a stable and effective heterogeneous nanocatalyst under optimized reaction conditions. Overall, our findings demonstrate that the nanoparticles possess significant promise as a robust and efficient heterogeneous nanocatalyst when the reaction parameters are appropriately controlled.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eUpon illumination of the semiconductor (1% La-BFO) with light energy matching or exceeding its band gap, electrons are excited to the conduction band (CB), leaving behind holes in the valence band (VB) (Eq.\u0026nbsp;2). These photogenerated holes (h\u003csup\u003e+\u003c/sup\u003e) can then react with water molecules to produce highly reactive hydroxyl radicals (\u003csup\u003e\u0026bull;\u003c/sup\u003eOH) (Eq.\u0026nbsp;3), while the excited electrons reduce dissolved oxygen in the water, leading to the formation of superoxide anion radicals (O\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e\u0026bull;\u0026minus;\u003c/sup\u003e) (Eq.\u0026nbsp;4). These radicals subsequently participate in the partial or complete degradation of the ibuprofen (IBU) molecule. A comparison study described in a tabular form in table 1.\u003c/p\u003e \u003cp\u003eThe integration of La nanoparticles onto the BFO surface results in the formation of a heterojunction at the metal-semiconductor interface, characterized by a rectifying contact. Under thermal equilibrium, the Fermi energy levels of both materials align, causing electrons to transfer from the semiconductor to the metal (La work function, ϕLa\u0026thinsp;=\u0026thinsp;2.85 eV), which is lower than that of the semiconductor (BiFeO\u003csub\u003e3\u003c/sub\u003e work function\u0026thinsp;\u0026asymp;\u0026thinsp;4.7 eV). This rectifying contact, with a downward bending of the semiconductor's energy bands, facilitates the movement of electrons into the metal. Consequently, when the La-BFO composite is exposed to light, the photogenerated electrons tend to migrate towards the La nanoparticles. The metallic La acts as an efficient electron scavenger, thereby hindering the undesirable recombination of photogenerated electrons and holes (e\u003csup\u003e\u0026minus;\u003c/sup\u003e - h\u003csup\u003e+\u003c/sup\u003e). Furthermore, La nanoparticles exhibit surface plasmon resonance (SPR) upon absorbing visible light, which can also contribute to the generation of superoxide anion radicals (O\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e\u0026bull;\u0026minus;\u003c/sup\u003e). During the photocatalytic degradation of ibuprofen, these superoxide anion radicals can initiate decarboxylation, leading to the formation of isobutyl acetophenone as an intermediate, which is further transformed into p-Isobutyl-phenol as the primary product. Additionally, the presence of hydroxyl radicals (\u003csup\u003e\u0026bull;\u003c/sup\u003eOH) promotes hydroxylation reactions, resulting in the formation of 1-(4-isobutylphenyl) ethanol, which then undergoes demethylation to also yield p-Isobutylphenol.\u003c/p\u003e \u003cp\u003eLa-BiFeO\u003csub\u003e3\u003c/sub\u003e\u0026thinsp;+\u0026thinsp;hν \u0026rarr;e\u003csup\u003e\u0026minus;\u003c/sup\u003e+h\u003csup\u003e+\u003c/sup\u003e (2)\u003c/p\u003e \u003cp\u003eh\u003csup\u003e+\u003c/sup\u003e +H\u003csub\u003e2\u003c/sub\u003eO \u0026rarr;OH.+H\u003csup\u003e+\u003c/sup\u003e (3)\u003c/p\u003e \u003cp\u003ee\u003csup\u003e\u0026minus;\u003c/sup\u003e +O\u003csub\u003e2\u003c/sub\u003e \u0026rarr;O\u003csub\u003e2\u003c/sub\u003e.\u003csup\u003e\u0026minus;\u003c/sup\u003e (4)\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"No\" id=\"Taba\" border=\"1\"\u003e \u003ccolgroup cols=\"7\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c7\" colnum=\"7\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eSL.No.\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eCatalyst\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eAmount\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eLight Source\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eTime\u003c/p\u003e \u003cp\u003e(min)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c6\"\u003e \u003cp\u003e%D\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c7\"\u003e \u003cp\u003eRef.\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eZnO\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e1g/L\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003eUV\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e60\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e86.6\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e[\u003cspan citationid=\"CR51\" class=\"CitationRef\"\u003e51\u003c/span\u003e]\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eTiO\u003csub\u003e2\u003c/sub\u003e and ZnO\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e1mg\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003eUV/LED\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e90\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e99.99\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e[\u003cspan citationid=\"CR52\" class=\"CitationRef\"\u003e52\u003c/span\u003e]\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003ePd-TiO\u003csub\u003e2\u003c/sub\u003e/ZSM-5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e0.17gL\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003eUVC irradiation\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e300\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e59.7\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e[\u003cspan citationid=\"CR53\" class=\"CitationRef\"\u003e53\u003c/span\u003e]\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eTiO\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e0.03 g\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003emercury lamp (125 W)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e100\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e[\u003cspan citationid=\"CR54\" class=\"CitationRef\"\u003e54\u003c/span\u003e]\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eCu/Ag\u0026ndash; BiVO4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003evisible-light irradiation\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e300\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e89 and 96\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e[\u003cspan citationid=\"CR55\" class=\"CitationRef\"\u003e55\u003c/span\u003e]\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e6\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eLa-BiFeO\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e0.03g\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003eSolar light\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e90\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e89\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003eCurrent work\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e"},{"header":"6. Conclusion","content":"\u003cp\u003eLanthanum-doped bismuth ferrite (La-BFO) was produced using an ecologically benign approach. The X-ray diffraction (XRD) patterns revealed the distinctive peaks associated with bismuth ferrite's rhombohedral crystal structure. The addition of lanthanum nanoparticles to the surface of BiFeO\u003csub\u003e3\u003c/sub\u003e reduced the absorbance of the La-BFO nanocomposites, implying a further reduction in bismuth ferrite. Photocatalytic assessments revealed that in alkaline settings, the La-BFO nanocomposites produced byproducts during the experiment's early phases. Lanthanum functions as an electron scavenger, reducing electron-hole recombination and promoting the creation of byproducts. Furthermore, the pH of the solution impacted ibuprofen (IBP) adsorption onto La-BFO, with neutral circumstances producing more intermediate compounds than alkaline and acidic conditions, respectively.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eAcknowledgment\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe authors are appreciative to the department of chemistry at ITER, Siksha \u0026apos;O\u0026apos; Anusandhan (Deemed to Be University), Bhubaneswar for providing laboratory space for this work. We thank various research centers, including Kalinga Institute of Industrial Technology and National Institute of Technology\u0026nbsp;Rourkela, for sharing their analytical techniques.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eFunding:\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eNo funding\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAuthor information:\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAuthors and affiliations\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eDepartment of Chemistry,ITER, Siksha \u0026lsquo;O\u0026rsquo; Anusandhan (Deemed to be University) Bhubaneswar, Odisha 751030, India.\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eRasmirekha Pattanaik, Rishabh Kamal, Debapriya Pradhan, Suresh Kumar Dash\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eDepartment of Chemistry,\u003cem\u003eCenturion University\u003c/em\u003e of Technology and Management, Bhubaneswar, Odisha,\u0026nbsp;\u003c/strong\u003e\u003cstrong\u003e761211\u003c/strong\u003e\u003cstrong\u003e, India.\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eDebapriya Pradhan\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAuthors\u0026rsquo; contribution:\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eRasmirekha Pattanaik conducted the experiments, collected the data, prepared the manuscript, and handled the characterization work. Suresh Kumar Dash provided critical insights, developed the research concept, and guided the project to completion. Debapriya Pradhan and Rishabh Kamal were engaged in the analysis of the data.\u003cbr\u003e\u0026nbsp;All authors contributed significantly throughout the course of the study. The final manuscript was read and approved by all contributors.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eMaterials and Data availability\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eAll data generated or analyzed during this study are included within this article. Additional data can be made available upon request.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eCorresponding author\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eCorresponds to Suresh kumar dash\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eClinical trial number\u003c/strong\u003e: not applicable\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eEthics declarations\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eEthics approval and consent to participate\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eNot applicable\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eConsent for publication\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eNot applicable\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eCompeting Interest\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe authors declare no known financial or personal conflicts of interest that could have influenced the outcomes of this research.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n\u003cli\u003eLaermann-Nguyen U, Backfisch M (2021d) Innovation crisis in the pharmaceutical industry? 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Chemosphere 117:527\u0026ndash;531. https://doi.org/10.1016/j.chemosphere.2014.09.017\u003c/li\u003e\n\u003c/ol\u003e"},{"header":"Schemes","content":"\u003cp\u003eSchemes 1 and 2 are available in the Supplementary Files section.\u003c/p\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"discover-applied-sciences","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"","sideBox":"Learn more about [Discover Applied Sciences](https://link.springer.com/journal/42452)","snPcode":"42452","submissionUrl":"https://submission.springernature.com/new-submission/42452/3","title":"Discover Applied Sciences","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"Discover Series","inReviewEnabled":true,"inReviewRevisionsEnabled":true},"keywords":"Moringa oleifera Lam, Leaves, Green synthesis, La-BiFeO 3, Drugs, Mechanism","lastPublishedDoi":"10.21203/rs.3.rs-6543925/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-6543925/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eIbuprofen is a potential environmental toxin and carcinogen for freshwater ecosystems, posing significant risks to human health, particularly through its impact on kidney function. This research introduced a new type of bismuth ferrite perovskite material, modified with separable lanthanum, to explore how sunlight can be used to break down ibuprofen in water. The catalysts used in the study were created through green synthesis and co-precipitation methods, and their characteristics were analyzed using various techniques like X-ray diffractometry (XRD), Field Scanning emission microscopy (FE-SEM), X-ray photoelectron spectroscopy(XPS), UV-VIS absorption spectroscopy(UV-DRS) and Photoluminescence spectra(PL). The research explored the effect of photocatalysis on ibuprofen degradation. Pseudo-first-order kinetic model were used to assess the degradation rate of ibuprofen. The addition of 1% lanthanum to BiFeO\u003csub\u003e3\u003c/sub\u003e increased the material's surface area and pore capacity significantly, resulting increase in photocatalytic ibuprofen mineralization efficiency. The paper also provides a probable mechanism for how lanthanum doping effects the formation of BiFeO\u003csub\u003e3\u003c/sub\u003e nanoparticles and their photocatalytic activity based on experimental data. The catalytic properties of the bio-synthesized La-BFO nanoparticles were then assessed by their ability to degrade under various laboratory conditions. This demonstrates that the phytochemical from moringa oleifera provides an inexpensive and environmentally friendly approach for synthesizing catalytic nanoparticles that can break down highly toxic drugs.\u003c/p\u003e","manuscriptTitle":"Fabrication of Green synthesized Lanthanum-Doped Bismuth Ferrite Perovskite type Nanocomposite for Photocatalytic Removal of Ibuprofen from Aqueous Solution","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-05-12 09:33:14","doi":"10.21203/rs.3.rs-6543925/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Revision requested","date":"2025-05-14T09:11:25+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-05-13T16:22:49+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-05-13T06:32:03+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-05-12T06:16:47+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"32063049911393172628801298605483563129","date":"2025-05-07T11:02:52+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"229685169448081738160479472581196630504","date":"2025-05-07T10:29:43+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"186163998495000138754248025742045164971","date":"2025-05-07T08:12:16+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2025-05-07T06:35:49+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2025-05-03T02:40:41+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2025-05-03T02:39:16+00:00","index":"","fulltext":""},{"type":"submitted","content":"Discover Applied Sciences","date":"2025-04-28T04:56:11+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"discover-applied-sciences","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"","sideBox":"Learn more about [Discover Applied Sciences](https://link.springer.com/journal/42452)","snPcode":"42452","submissionUrl":"https://submission.springernature.com/new-submission/42452/3","title":"Discover Applied Sciences","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"Discover Series","inReviewEnabled":true,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"4b8e0a8c-15d8-4875-8d53-861b45a53788","owner":[],"postedDate":"May 12th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"under-review","subjectAreas":[],"tags":[],"updatedAt":"2025-06-11T09:53:14+00:00","versionOfRecord":[],"versionCreatedAt":"2025-05-12 09:33:14","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-6543925","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-6543925","identity":"rs-6543925","version":["v1"]},"buildId":"XKTyCvWXoU3ODBz1xrDgd","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}