Dual-Metal-Doped Perovskite Adsorbents for Efficient Removal of Humic Acid

Dual-Metal-Doped Perovskite Adsorbents for Efficient Removal of Humic Acid | 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 Article Dual-Metal-Doped Perovskite Adsorbents for Efficient Removal of Humic Acid Ze-Xian Low, Lekai Zhao, Shuang Han, Xiao Ma, Ming Zhou, Qiuyue Wang, and 3 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-5225322/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 12 Mar, 2026 Read the published version in Nature Communications → Version 1 posted You are reading this latest preprint version Abstract Humic acid (HA), a complex organic compound of natural matter, is harmless on its own but can form carcinogenic disinfection byproducts such as trihalomethanes and haloacetic acids during water chlorination and disinfection processes, posing serious risks to aquatic organisms and human health. We present a B-site dual-metal-doping strategy to fabricate ferromagnetic perovskite-type adsorbents for rapid and efficient HA degradation. Through B-site modification with Ti and Co, the resulting perovskite absorbent exhibits a rapid HA adsorption rate with a high adsorption capacity of 381 mg/g. We demonstrate that the adsorbent can be regenerated in situ or magnetically recovered for Fenton regeneration. The dynamic adsorption behavior of HA is accurately described and predicted by the Bed Depth Service Time (BDST), Thomas, and Yoon-Nelson models while computational simulations provide insights into the interactions between the perovskite adsorbent and HA molecules. Our findings reveal the potential of perovskite materials as highly effective catalytic adsorbents for organic compounds that can be efficiently regenerated, paving the way for their development in water remediation applications. Physical sciences/Engineering/Chemical engineering Physical sciences/Chemistry/Chemical engineering perovskite oxide B-site doping humic acid dynamic adsorption Fenton Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Introduction With the expanding global population and diminishing freshwater resources, developing advanced wastewater treatment and reuse technologies has become critically important for sustaining water availability 1 – 3 . Among the water contaminants, humic acid (HA)—formed from the decay of plant and animal matter—significantly contributes to natural organic matter (NOM) in freshwater 4 – 8 . HA is a high molecular weight organic substance with a complex and stable structure that is refractory and resists biodegradation under natural conditions 9 , 10 . If left untreated, HA in water supplies can form stable complexes with heavy metal ions, enhancing their persistence and mobility, which leads to the accumulation of pollutants in sediments and organisms 11 – 16 . Furthermore, during chlorination, HA can form carcinogenic, teratogenic, and mutagenic disinfection byproducts such as trihalomethanes and haloacetic acids, severely compromising water quality and human health 17 – 22 . Hence, the effective removal of HA during wastewater treatment processes is crucial for ensuring safe and clean water. Currently, three main approaches exist for HA removal: biological methods (e.g., biological treatment 23 – 25 ), chemical methods (e.g., electrolysis 26 , flocculation/coagulation 27 , and catalytic oxidation 28 – 30 ), and physical methods (e.g., membrane filtration 31 , 32 and adsorption 33 , 34 ). Among these, adsorption is widely employed due to its cost-effective, simple design, operation ease, environmental friendliness, and high efficiency 35 . However, traditional adsorbents such as resins and activated carbon are limited by their low adsorption capacity, low specific surface area, and poor regeneration properties 36 , 37 . Perovskite oxides, represented by the formula ABO 3 , are a diverse family of mixed metal oxides renowned for their highly tunable compositions and physicochemical properties, making them suitable for a wide range of applications, including solar cells 38 , 39 , fuel cells 40 , 41 , electromagnetic materials 42 – 44 , chemical sensors 45 , and catalysts 46 , 47 . In these crystalline structure, A-site elements—typically rare earth metals or alkaline earth metals (e.g., La, Pr, Gd) characterized by larger ionic radii—occupy the central position of the cubic lattice, while B-site elements—usually transition metals (e.g., Ti, Mn, Fe, Co, Cr) with smaller ionic radii—occupy corner-sharing octahedra 48 . A distinguishing feature of perovskite oxides is their unique structural tunability and design flexibility, which allows for the customization and enhancement of specific properties 49 . For instance, Ti doping in LaFeO 3 perovskites via a sol-gel method, enhances catalytic activity, resulting in improved removal and mineralization rates of chlorophenols 50 . Ti doping also augments magnetic properties by influencing the Fe spin through the unpaired electrons of Ti 3+ ions 51 . Similarly, Co doping introduces abundant active sites that accelerate methane activation, while Sr doping increases oxygen vacancies, facilitating the migration of oxygen anions for enhanced reactivity and resistance to coking 52 . Transition metal doping at the B site can create electron-deficient states, leading to the formation of oxygen vacancies. Specifically, dual doping exploits complementary effects between metal ions of differing ionic radii, simultaneously enhancing multiple properties and improving material stability for extended use 53 , 54 . We hypothesize that targeted doping strategies can tailor perovskite materials into high-performance adsorbents with enhanced adsorption capacities and regenerative functionalities essential for efficient and sustainable wastewater treatment processes. Here we present a dual-doping strategy for the fabrication of perovskite-type adsorbent aimed at effectively remediating HA-contaminated water. By simultaneously doping Ti and Co at the B-site of LaFeO 3 , we developed an adsorbent (LFTCO) that demonstrates rapid and enhanced HA adsorption, as confirmed through dynamic adsorption studies and mechanistic modeling. We further demonstrate that this Fenton-active adsorbent can be regenerated in situ as part of a continuous process or magnetically recovered for subsequent chemical regeneration. The LFTCO adsorbents exhibited excellent performance stability for HA adsorption and chemical regeneration over 280 hours in a continuous adsorption-regeneration cycle, all while maintaining their crystalline structure. This unique stability enables an energy-efficient, one-step regeneration process, setting it apart from traditional methods that require high-temperature calcination or solvent elution. Results and discussion Fabrication of LFTCO absorbents As a typical ABO 3 -type perovskite oxide, LaFeO 3 has an atomic ratio of approximately 1:1:3 for La, Fe, and O 55 , 56 . In the case of dual-doped LFTCO, La occupies the A-site, while Fe, Co, and Ti occupy the B-site (Fig. 1 a). The LF 0.55 T x C 0.45−x O (x = 0.1, 0.2, 0.3, and 0.4) oxides were successfully synthesized using a facile sol-gel method. The resulting perovskite oxide-type adsorbents exhibited uniform block-like porous structure (Fig. 1 b, Supplementary Fig. S2a-d) and the HRTEM image (Fig. 1 c) depicted lattice fringes of 0.28 nm, corresponding to the (110) plane of LaFeO 3 . Elemental composition analysis using energy dispersive X-ray spectroscopy (Supplementary Fig. S2e) confirmed an atomic ratio of La: (Fe + Ti + Co): O was approximately 1:1:3, verifying the successful synthesis of LFTCO via the sol-gel method. X-ray diffraction spectroscopy (Fig. 1 e) revealed that the diffraction peaks of LFTCO closely matched the characteristic peaks of LaFeO 3 (JCPDS no. 75–0541), consistent with its crystal structure, which was also confirmed by the selected area electron diffraction (SAED) pattern (Fig. 1 d) 57 , 58 . Analysis of the (110) crystal plane (Fig. 1 f) showed that as the Ti doping ratio increased, there was an overall left shift in the diffraction peaks, indicating an increase in crystal plane spacing 59 . Interestingly, at a doping ratio of x = 0.3, the diffraction peak shifted to its original position, maintaining the original configuration of LeFeO 3 . This shifting phenomenon, attributed to changes in the metal-oxygen bond lengths induced by doping, suggest that Ti/Co double doping can stabilize the perovskite crystal configuration. FTIR spectroscopy (Fig. 1 g) revealed peaks at approximately 576 cm − 1 , indicating the presence of metal oxide bonds, specifically attributed to the Fe-O stretching vibration characteristic of the octahedral FeO 6 group in LaFeO 3 60 . Most adsorbents are difficult to separate from wastewater streams, which poses challenges for their reuse. Consequently, the magnetic separation of suspended adsorbents has been extensively researched 61 . The ferromagnetic properties of the synthesized perovskite oxides was evaluated using M-H curves, as shown in Fig. 1 h and Supplementary Table S1 with the saturation magnetization measured as the primary indicator of their recovery capability 62 . As the Ti doping ratio increased, the magnetization initially increased and then decreased. In LFTCO, Ti can exchange-couple with Fe, shifting the Fe spin moment, which facilitates small-angle rotation tilt, thereby enhancing overall ferromagnetism due to uncompensated Fe spins. Surface oxygen vacancies disturb the antiparallel spin ordering in Fe 3+ -O-Fe 3+ and Fe 4+ -O 2 -Fe 4+ through super-exchange interactions, leading to increased magnetization. As the Fe spin moment increases, the presence of uncompensated spins allows free motion of the domain walls, further enhancing magnetization. However, high concentrations of nonmagnetic Ti can inhibit domain wall motion, resulting in decreased magnetization 63 . The results indicated that LFTCO-0.3 and LFTCO-0.2 exhibited strong ferromagnetic behavior (Ms = 7.36 emu/g and 5.24 emu/g, respectively), which is advantageous for recycling and utilization in water treatment processes 64 . To further elucidate the effect of Ti/Co doping on the magnetic properties of the materials, we performed theoretical validation using Density Functional Theory (DFT) calculations. LaFeO 3 is a G-type antiferromagnetic crystal, and its weak magnetism observed experimentally has been attributed to Oxygen vacancies introduced during synthesis (Fig. 1 i, l). Pristine LaFeO 3 crystals lack unpaired electrons, resulting in zero spin density throughout the crystal lattice, and are thus non-ferromagnetic. Introducing Co dopants significantly alters the electronic structure of the closed-shell LaFeO 3 crystal. This is due to the electronic configuration of Co (III), which is [Ar]4s 0 3d 6 . According to Hund's rule, the 3d orbitals of Co(III) have four unpaired electrons, leading to a net magnetic moment. The difference in the number of unpaired electrons compared to Fe(III) disrupts the originally stable G-type antiferromagnetic structure when Co is incorporated into the lattice. Figure 1 j, m show that Co-doped LaFeO 3 crystals exhibit prevalent spin density, indicating the potential to become paramagnetic or ferromagnetic materials. Conversely, higher doping levels of Ti reduces the magnetism of the system because the electronic configuration of Ti (III) is [Ar]4s 0 3d 1 , with only one unpaired electron in the 3d orbital. This results in a system with fewer unpaired electrons, leading to non-magnetism or weak ferromagnetism. Figure 1 k, n further confirm this, showing only one unpaired electron present in the system. Microstructure and metal ion state analysis of LFTCO absorbents The specific surface areas and pore size distributions of LFTCO, which influence its adsorption capacity and rate, were determined by N 2 sorption porosimetry. As shown in Fig. 2 a, the N 2 adsorption/desorption isotherms of LFTCO exhibited typical type IV curves with hysteresis between P/P 0 = 0.5 and 1.0, indicating a mesoporous structure 65 . The pore size distribution (Fig. 2 b) revealed that LFTCO had pore size ranging from 2 to 30 nm, with LFTCO-0.3 possessing the smallest pore size among them. These results indicate that LFTCO-0.3 had the largest specific surface area. Further analysis of pore volume showed that LFTCO-0.3 had the highest total pore volume of 0.040 cm 3 ·g − 1 (Supplementary Table S1 ). This suggests that LFTCO-0.3 could exhibit enhanced adsorption compared to other LFTCO samples. We performed XPS to determine the surface chemical composition and chemical states of LFO and LFTCO-0.3 (Fig. 2 c-f). The XPS survey spectra (Fig. 2 c) confirm that Ti and Co are successfully doped into the LFTCO-0.3 lattice. The A-site La element, which stabilizes the crystal structure, is present as La 3+ (Supplementary Fig. S3a). The characteristic peaks of Ti 2p at 458.1 eV and 463.8 eV correspond to Ti 2p 3/2 and Ti 2p 1/2 of Ti 4+ , respectively (Supplementary Fig. S3b). Compared to LFO, the Fe 2+ /Fe 3+ ratio increases (Fig. 2 d), and the redox dynamics between Fe 2+ /Fe 3+ and Co 2+ /Co 3+ promote the generation of surface oxygen vacancies to maintain charge neutrality. This is further confirmed by the O 1s XPS spectrum (Fig. 2 f), where peaks below 530 eV correspond to lattice oxygen and peaks above 530 eV correspond to chemisorbed oxygen 66 . Compared to LFO, the increased ratio of lattice oxygen to chemisorbed oxygen in LFTCO-0.3 indicates that Ti/Co doping promotes the creation of more oxygen vacancies in the LFO lattice, thus improving the adsorption performance of the material 67 . Static HA adsorption on LFTCO adsorbent Using HA as the target contaminant, Supplementary Fig. S4 illustrates the differences in adsorption performance among various adsorbents: unmodified (LFO), single-doped (LFTO and LFCO), and dual-doped (LFTCO). The removal rates of HA in water revealed that adsorption efficiency improved with the doping of Ti and Co metals, with the dual-doped LFTCO demonstrating the most significant effect. Among these, LFTCO-0.3 exhibited the highest adsorption performance. This improvement is attributed to dual doping at the B sites, which effectively enhances the specific surface area, increases the number of adsorption sites for pollutant molecules, and promotes the formation of oxygen vacancies on the surface of lanthanum ferrite. These oxygen vacancies enhance electron mobility and chemical activity, further boosting adsorption. Consequently, LFTCO-0.3 was selected for subsequent experiments. Adsorption experiments were carried out with different concentrations of HA ( C HA = 10, 30, and 50 mg/L) at a fixed adsorbent dosage ( C ads = 0.2 g/L) and pH = 7 to compare the removal efficiency and adsorption capacity, aiming to identify the dual-doped perovskite oxide adsorbent with optimal performance (Supplementary Text S2). The results showed that all dual-doped LFTCO samples exhibited excellent adsorption for HA. Notably, LFTCO-0.3 demonstrated higher removal efficiency across different concentrations compared to other doping ratios (Fig. 3 a), likely due to its largest specific surface area and smallest pore size among all dual-doped modified adsorbents (Fig. 2 b and Supplementary Table S1 ). As the HA concentration increased, the adsorption sites were more fully utilized, further enhancing the adsorption effect. When the concentration of HA increased from 10 to 30 mg/L, the adsorption capacity of LFTCO-0.3 increased significantly. However, as the HA concentration was increased to 50 mg/L, the increase in adsorption capacity became less pronounced (Supplementary Fig. S5). Therefore, for subsequent experiments exploring varying conditions, an HA concentration of 30 mg/L was selected. The amount of adsorbent is a critical factor affecting adsorption performance. As shown in Fig. 3 b, the HA removal efficiency by LFTCO-0.3 increased with an increase in adsorbent dosage. When the adsorbent dosage was raised from 0.1 g/L to 0.2 g/L, the removal efficiency of HA significantly increased from 82–97%. However, further increasing the dosage to 0.4 g/L only marginally increased the removal efficiency to 99%. This plateau is attributed to adsorbent aggregation at higher dosages, which reduces the accessible surface area and decreases the total number of active adsorption sites. Additionally, the limited number of HA molecules relative to the increased adsorbent restricts further improvements in removal efficiency. Meanwhile, the adsorption capacity gradually decreased as the adsorbent dosage increased from 0.1 to 0.4 g/L. This reduction is due to the presence of unsaturated adsorption sites at higher dosages, leading to a decrease in per-unit adsorption capacity. Considering both the removal efficiency and adsorption capacity, 0.2 g/L was selected as the optimal adsorbent dosage. To optimize the adsorption process for a wide range of real-world wastewater conditions, the effect of pH on adsorption was investigated (Fig. 3 c). The adsorption performance of LFTCO-0.3 under various acidic and alkaline conditions is influenced by three primary factors: the surface charge of the adsorbent, the solubility of HA, and changes in HA molecular configuration 68 , 69 . The results indicated that the removal performance of HA by LFTCO-0.3 gradually increased as the solution pH ranged from 3 to 7. Under acidic conditions, HA molecules tend to polymerize and often exist as undissociated molecules or weakly ionic species, resulting in lower solubility. This enhances the interaction between HA and the adsorption sites on LFTCO-0.3, thereby improving the adsorption performance. Combined with the Zeta potential measurements (Fig. 3 d), it was found that LFTCO-0.3 forms electrostatic attractions with negatively charged anions (HA + H 2 O→H 3 O + +A − ), promoting adsorption under acidic conditions 70 , 71 . As the pH increased from 7 to 11, the removal efficiency of HA by LFTCO-0.3 gradually decreased. This reduction is primarily due to electrostatic repulsion between the negatively charged adsorbent surface and HA molecules under alkaline conditions. Additionally, the increased solubility of HA in alkaline solutions further diminishes the adsorption capacity of LFTCO-0.3 72 . Hence, LFTCO-0.3 demonstrated notably effective adsorption performance for HA under both acidic and neutral conditions. Considering that the pH of HA solutions is generally around 7, the highest adsorption performance of LFTCO-0.3 at pH 7 indicates that highly efficient removal of HA can be achieved without the need for pH adjustment. Electrostatic modulation and thermodynamic insights into HA adsorption mechanisms To investigate the enhanced adsorption and reaction mechanisms between HA and LFTCO-0.3, quantum chemical calculations were performed on HA molecules (Fig. 3 g). The results revealed significant differences in the electrostatic potential properties of HA molecules under various protonation states, corresponding to different pH conditions. At lower pH levels, both carboxyl groups of the HA molecule are protonated and electrically neutral. The electrostatic potential projection on its van der Waals surface shows a maximum surface electrostatic potential is 61.934 kcal/mol and a minimum of -39.613 kcal/mol, indicating significant polarization. The negatively charged regions are located near the carboxyl and nitro groups, while the positively charged regions are near the saturated cycloalkane structures. As the ambient pH increases, the HA molecule undergoes further ionization. At least one of the carboxyl groups becomes deprotonated, imparting a negative charge to the molecule. The van der Waals surface potentials becomes entirely negative, with the highest value decreasing to -5.270 kcal/mol and the lowest to -148.126 kcal/mol. With a further decrease in ambient proton concentration, the maximum electrostatic potential shifts to -39.613 kcal/mol. If the ambient proton concentration is reduced even further, all active hydrogens on the HA molecules dissociate, significantly enhancing the molecule's negative charge. The van der Waals surface then exhibits strong negative potential, with the highest being − 80.309 kcal/mol and the lowest − 242.539 kcal/mol. These calculations indicate that HA molecules tend to adsorb onto positively charged sites of the adsorbents due to electrostatic interactions. Consistent with the zeta potential test results, the increase in pH leads to HA molecules becoming more electronegative. Thus, as pH increases from 3 to 7, the enhanced negative charge of HA strengthens the electrostatic attraction with the positively charged surface of LFTCO-0.3, enhancing their removal from water. However, as the pH continues to increase beyond 7, the removal efficiency significantly decreases. This reduction is primary due to the adsorbent surface becoming less positively charged or even negatively charged at higher pH levels, leading to electrostatic repulsion between the adsorbent and the negatively charged HA molecules. Furthermore, it was demonstrated that LFTCO-0.3 not only possesses a wide range of adsorption adaptability but also exhibits excellent removal performance for various types of contaminants in water, especially for anionic contaminants (Supplementary Fig. S6). The adsorption kinetics depend on the physical and chemical properties of the adsorbent, which influence the adsorption mechanisms. To model the experimental data of HA adsorption onto LFTCO-0.3, pseudo-first order kinetic (PFO), pseudo-second order kinetic (PSO), and intra-particle diffusion (ID) models were employed (Supplementary Text S2) 73 . The fitting curves are shown in Fig. 3 e and Supplementary Fig. S7b-c, and the corresponding kinetic parameters are presented in Supplementary Table S2. The ID model fitting yield correlation coefficients (R 2 ) ranging from 0.341 ~ 0.945, indicating that intra-particle diffusion was not the rate-determining step in the adsorption process 74 . In comparison, the PFO model showed lower correlation with the experimental data (R 2 = 0.834 ~ 0.990) than the PSO model, which exhibited an excellent fit with high correlation coefficients (R 2 > 0.996). Additionally, the equilibrium adsorption capacities calculated using the PSO kinetic equation (Supplementary Equation S4) were consistent with the experimental data. Therefore, the adsorption of HA onto LFTCO-0.3 is better described by the PSO model, suggesting that the adsorption process is predominantly governed by chemisorption, with physisorption playing a secondary role. To investigate the relationship between adsorption capacity and equilibrium concentration, both Langmuir and Freundlich isotherm models were applied 75 . The correlation coefficients (R 2 ) and corresponding parameters for both models are listed in Fig. 3 f and Supplementary Table S3. The Langmuir model, with a correlation coefficient of R 2 = 0.983, provided a better fit to the experimental data better than the Freundlich model (R 2 = 0.979). This indicates that the adsorption process follows monolayer adsorption, primarily characterized by chemisorption 76 . Thermodynamic analysis further elucidated the significant role of temperature in the adsorption process from an energy perspective. For practical applications, thermodynamic changes were studied at 298 K, 308 K, and 318 K. As the adsorption temperature increased, the adsorption performance of LFTCO-0.3 for HA improved, and the thermodynamic equilibrium constant ( K d ) also increased. The results (Fig. 3 h and Supplementary Table S4) showed that ∆G < 0, indicating that the adsorption process is spontaneous and fall within the range of physical and chemical adsorption (-20 ~ -40 kJ·mol − 1 ) 77 . Furthermore, the absolute value of ∆G increased with increasing temperature, confirming the spontaneity of the adsorption process at higher temperatures. The positive value of ∆S suggests an increase in the enthalpy at the solid-liquid interface during adsorption, reflecting greater dispersal and interaction of HA molecules on the LFTCO-0.3 interface. This enhanced the solid-liquid interfacial area, promoting further adsorption. Additionally, ∆H > 0 indicates that the adsorption process is endothermic, implying that higher temperatures favor adsorption. These results demonstrated that the adsorption of HA onto LFTCO-0.3 is a spontaneous, endothermic chemical process with improved performance at elevated temperatures. Hydrophilicity and structural defects in LFTCO adsorbent Low-Field Nuclear Magnetic Resonance (LF-NMR) was used to quantify the surface hydrophilicity of water trapped in the absorbents. Compared to pure water, the presence of the adsorbent causes the water to enter nanoconfined regions. The LF-NMR characterization revealed that the T 2 relaxation times of LFO and LFTCO were 932.4 and 142.8 ms, respectively (Fig. 3 i). Given equal amounts of adsorbent and solvent in both samples, the transverse relaxation time (T 2 ) exhibited a negative correlation with the bound water content 78 . From LFO to LFTCO-0.3, protons adsorbed on the particle surfaces become more tightly bound, significantly shortening the NMR relaxation time and increasing the bound water content. This increase is primarily due to the improved hydrophilicity of the LFTCO-0.3 surface achieved through doping modification. The presence of more bound water on and within the adsorbent indirectly enhances its adsorption properties. This finding aligns with the type and content of surface oxygen in perovskite oxides determined by XPS O 1s spectroscopy (Fig. 2 f). The ratio of oxygen vacancies to lattice oxygen (O V /O L ), which indicates the abundance of oxygen vacancies in the material, increased from 0.61 in LFO to 1.05 in LFTCO-0.3 (Supplementary Table S5). The dual doping of Ti and Co in LFTCO-0.3 promotes the formation of structural defects, generating more oxygen vacancies and active sites, thereby improving adsorption performance. Compared with LFO, LFTCO-0.3 possesses a larger number of oxygen vacancies and active sites, significantly enhancing its adsorption capacity. The Independent Gradient Model based on Hirshfeld partition (IGMH) is a computational interaction method that utilizes the electron density gradient and has gained widespread popularity due to its universality and robustness. We applied IGMH to calculate the adsorption behavior of HA molecules on the surface of LaFeO 3 crystals. The results indicate that pristine LaFeO 3 crystals possess notable adsorption capacity for HA molecules (Fig. 3 j), mainly driven by interactions between Fe and O atoms, with HA molecules being adsorbed onto the crystal surface through two or more Fe-O interactions. As discussed previously, Co doping leads to a transition of the crystal material from an antiferromagnetic to a ferromagnetic state. Given that closed-shell organic molecules like HA are diamagnetic, the enhanced adsorption performance of HA on the Co-doped LaFeO 3 surface is relatively modest (Fig. 3 k). In contrast, Ti doping reverts the material back to an antiferromagnetic state, restoring these interactions. Due to the B-site dual-doping of Co and Ti during synthesis, the number of adsorption sites and anisotropy of the crystal increase, leading to a stronger adsorption capacity compared to the pristine LaFeO 3 crystals (Fig. 3 l). The dual-doping effectively enhances the crystal’s ability to adsorb HA molecules, showcasing a notable improvement in adsorption performance. Dynamic HA adsorption and model analysis on LFTCO To simulate real-world applications of adsorbents, we systematically investigated the influence of influent flow rate, bed height, feed concentration, and feed pH on the dynamic adsorption performance of LFTCO-0.3 (Fig. 4 a and Supplementary Text S3). The breakthrough curves under various conditions exhibited an S-shaped profile, indicating similar trends across different parameters. Over time, all adsorption curves followed a pattern characterized by an initial gentle slope, transitioning to a steep incline, and subsequently leveling off (Fig. 4 c-f). The flow rate significantly influences the contact time between the adsorbent and the pollutant during dynamic adsorption, thereby affecting the overall adsorption efficiency. We examined the effect of different influent flow rates ranging from 0.7 to 4.0 mL/min at fixed HA concentration and bed height (Fig. 4 c). At lower flow rates, the contact time between HA molecules and LFTCO-0.3 increased, allowing for more prolonged and effective interactions. Conversely, higher flow rates shortened the contact time, limiting external mass transfer to the adsorbent surface 79 . This resulted in the rapid passage of HA solution through the fixed bed column, decreasing interaction time and consequently lowering adsorption efficiency, which led to higher effluent concentrations. Furthermore, higher flow rates caused a greater volume of HA solution to pass through the adsorbent per unit time, thereby shortening the breakthrough time. As the flow rate increased, both the breakthrough and adsorption saturation points shifted to the left, resulting in shorter breakthrough and saturation times. In addition, with increasing flow rate, the adsorption capacity at saturation gradually decreased. Based on these observations, a flow rate of 1.4 mL/min was selected as the optimal condition for subsequent experiments. The bed height, which determines the amount of adsorbent in the column, plays a crucial role in the dynamic adsorption process. An increase in bed height results in more active adsorption sites, enhancing the treatment capacity for polluted wastewater and reducing the frequency of desorption. To further examine this, we studied the influence of various bed heights on dynamic adsorption performance (Fig. 4 d). The results indicated that as the bed height increased, the breakthrough and adsorption saturation time also increased significantly. A larger bed height, associated with a greater amount of adsorbent, led to an increased total number of active sites within the fixed bed column. This enhancement facilitated longer and more substantial contact between HA and the adsorbent, contributing to improved adsorption capacity. An increase in bed height corresponded to a longer breakthrough time, a gentler slope of the breakthrough curve, and an enlarged mass transfer zone. These factors collectively enhanced the overall adsorption capacity. When selecting the optimal bed height, it is essential to consider the amount of adsorbent used, adsorption efficiency, operational time, and economic viability. Based on these considerations, a bed height of 2.4 cm was determined to be optimal for this experiment. Feed concentration is a key factor affecting the dynamic adsorption performance, as the concentration gradient between the pollutant and the adsorbent surface provides the driving force for mass transfer and promotes adsorption. As the feed concentration of HA increases, the corresponding breakthrough and adsorption saturation times decrease (Fig. 4 e). As the feed concentration rises, the slope of the breakthrough curve steepens, and the time to reach the breakthrough point shortens. This occurs because a larger concentration difference between the surface of LFTCO-0.3 and HA in solution creates a greater driving force for mass transfer, allowing HA molecules to more rapidly occupy the adsorption sites on the surface of LFTCO-0.3 80 . This accelerates the rate of adsorption, causing the breakthrough and saturation points to be reached more quickly. Considering the influence of feed concentration on adsorption saturation time, a concentration of 30 mg/L was selected for subsequent experiments. The pH of the feed solution also significantly affects the dynamic adsorption performance by influencing the charge interactions between the adsorbent and the adsorbate. Dynamic adsorption experiments were carried out at different pH levels to understand their impact on HA adsorption (Fig. 4 f). Under acidic conditions, LFTCO-0.3 exhibits an enhanced adsorption capacity for HA. Conversely, under alkaline conditions, the breakthrough time is significantly shortened, and the adsorption capacity for HA is reduced. This phenomenon aligns with previous analyses of electrostatic interactions, solubility, and morphological changes at different pH levels. The results indicate that LFTCO-0.3 is effective for HA treatment under acidic conditions. Given the complexity of the dynamic adsorption process, which involves multiple components (solvent, adsorbate, adsorbent) and numerous operating conditions, we utilized several widely recognized dynamic adsorption models to fit the breakthrough curve of HA adsorption onto LFTCO-0.3, aiming to better understand its behavior and underlying mechanisms (Supplementary Text S3). The Bohart-Adams Surface Diffusion-Time (BDST) model was employed to predict the breakthrough times for different bed heights using the breakthrough curve data. For our analysis, we performed data fitting for varying bed heights at fixed influent flow rate and feed concentration. The linear fitting results (Fig. 4 b) demonstrated a high degree of accuracy, with a regression coefficient R 2 of 0.998. Moreover, the errors between the predicted breakthrough times from the BDST model and the actual breakthrough times were less than 2% (Supplementary Table S6). To further validate the BDST model, we calculated theoretical breakthrough times at various feed concentrations and flow rates using the fitted equation and compared them with the actual data. The errors between the theoretical and actual breakthrough times remained consistently low, less than 4% and 7% (Supplementary Tables S7 and S8), respectively. These findings indicate that the BDST model is highly applicable for modeling the dynamic adsorption process of HA onto LFTCO-0.3 and can reliably predict breakthrough times under different solution flow rates and concentrations. The Thomas model was also applied to estimate the equilibrium adsorption capacity and adsorption rate constant for studying the adsorption kinetics. The Thomas model fitting parameters (Supplementary Table S9) revealed R 2 values greater than 0.971. The adsorption rate constant K Th decreased with increasing bed height, increased with rising flow rate and feed concentration, and varied nonlinearly with pH (Fig. 4 g-j). The concordance between experimental and theoretical adsorption capacities indicates that the Thomas model accurately describes the dynamic adsorption of HA onto LFTCO-0.3, suggesting that internal and external diffusion are not the primary rate-determining factors 81 . The Yoon-Nelson model was utilized to evaluate the time τ required for the effluent concentration of HA to reach half the feed concentration and the adsorption rate constant K YN . According to Supplementary Equation S15, time and ln (C t /(C 0 -C t )) were fitted linearly, and the fitting curves are shown in Fig. 4 k-n. The theoretical τ values indicated that the breakthrough time increased with bed height and decreased with higher influent flow rate and concentration, as well as increased pH, before stabilizing. The R 2 values for the fits were greater than 0.971, closely aligned with the Thomas model results (Supplementary Table S9). These findings confirm that the Yoon-Nelson model accurately predicts the breakthrough time and rate constant K YN for the adsorption process using LFTCO-0.3, making it a reliable method for modeling dynamic adsorption behaviors. Cyclic performance and regeneration of LFTCO adsorbent We evaluated the reusability of LFTCO-0.3 for the adsorption of HA to assess its potential for industrial applications. Figure 5 a illustrates a schematic diagram of the adsorption-desorption cycle. Under static condition at pH 7.0, 0.2 g/L of absorbent was added to 200 ml of HA solution ( C HA = 30 mg/L). After the adsorption process was complete, LFTCO-0.3 was recovered using a strong magnet. The adsorbent was then immersed in a diluted hydrogen peroxide (H 2 O 2 ) solution to facilitate chemical desorption, leveraging the Fenton properties inherent in ferrite to generate hydroxyl radicals that break down the adsorbed HA. Following three washes with deionized water and drying at 60℃, the adsorbent was reused in the next adsorption experiment. After five adsorption-desorption cycles, the removal efficiency of LFTCO-0.3 to HA remained at 89.87% (Fig. 5 b), demonstrating that the magnetic adsorbent retained its adsorption performance after chemical desorption. This also suggests that LFTCO-0.3 maintained its Fenton activity and magnetism throughout the cycles. To understand the molecular interactions, density functional theory (DFT) calculations were performed to determine the molecular orbital structure (Supplementary Fig. S8), which confirmed the feasibility of using H 2 O 2 for the oxidative removal of HA molecules. The calculations indicated favorable interactions between H₂O₂, LFTCO-0.3, and the adsorbed HA, facilitating the oxidative degradation of HA during the desorption process. Moreover, the concentrations of dissolved metal ion gradually decreased with each cycle. After the fifth cycle, the concentrations of La 3+ , Co 3+ , Fe 3+ , and Ti 4+ were 0.017 mg/L, 0.048 mg/L, 0.026 mg/L, and 0.012 mg/L, respectively (Supplementary Fig. S9). These levels are below the national wastewater discharge standards, indicating minimal leaching of metal ions during regeneration. Furthermore, the crystal structure of the perovskite adsorbent remained unchanged after five cycles, as confirmed by X-ray diffraction analysis, indicating good structural stability (Supplementary Fig. S10). To investigate the regeneration and stability performance of LFTCO-0.3 during the dynamic adsorption process, we conducted five cycles of adsorption-desorption experiments using a fixed bed column packed with LFTCO-0.3, as illustrated in Fig. 5 c. The breakthrough curves (Fig. 5 d) indicate that LFTCO-0.3 maintained high adsorption performance after five cycles. As the cyclic experiment progressed, both the time to reach the breakthrough point and the saturation time decreased, suggesting a reduced adsorption capacity of LFTCO-0.3 for HA. This reduction is likely due to incomplete desorption within a fixed recovery period of 20 min. Despite this, LFTCO-0.3 exhibits good stability and regenerative capability, as confirmed by X-ray diffraction analysis. Notably, LFTCO-0.3 ranks among the highest in adsorption capacities for HA when compared to other adsorbents reported in the literature (Fig. 5 e; Supplementary Table S10). It rapidly achieves HA removal with a maximum adsorption capacity of 381 mg/g under 2 hr (Supplementary Table S2; Detailed comparison and methodology are provided in the Supporting Information). In addition, traditional regeneration methods for reported adsorbents typically involve high-temperature calcination or solvent elution using agents like NaOH, resulting in elevated energy consumption and potential secondary pollution 82 – 84 . In contrast, our adsorbent can be regenerated in under 20 min (Fig. 5 d) through the Fenton reaction, facilitated by LFTCO’s ability to generate radicals. The impressive adsorption and regeneration properties of LFTCO-0.3 make it particularly suitable for use in adsorption columns. Its easy dispersion and straightforward magnetic separation also allow its application in existing AOP tanks without requiring structural modifications to sewage treatment facilities. The versatility of LFTCO-0.3 supports flexible application scenarios. These findings suggest that LFTCO-0.3 could serve as an environmentally friendly and magnetic adsorbent with excellent HA removal performance, offering significant advantages in ease of regeneration, stability, and reduced environmental impact compared to conventional adsorbents. Conclusions We developed LFTCO, a dual-doped perovskite oxide adsorbent synthesized via the sol-gel method, featuring Co and Ti doping at the B-site. LFTCO exhibits superior adsorption performance for NOM, particularly HA. Kinetic and thermodynamic analyses confirm that the adsorption mechanism is predominantly chemical, augmented by spontaneous endothermic physical interactions. Dynamic adsorption experiments demonstrate LFTCO’s effectiveness for continuous HA removal, with predictive modeling using BDST, Thomas, and Yoon-Nelson models providing reliable estimates for adsorption capacity and breakthrough times. LFTCO’s excellent Fenton catalytic activity and magnetic properties enable efficient regeneration and reuse through magnetic separation, fixed-bed adsorption, and the Fenton reaction. This process circumvents the high energy consumption and potential secondary pollution associated with traditional regeneration methods. The versatility of LFTCO allows seamless integrated into adsorption columns and AOP tanks without requiring structural modifications to existing sewage treatment plants. Its easy dispersion and straightforward magnetic separation further broaden its application potential in diverse wastewater treatment scenarios. Overall, LFTCO emerges as a highly promising adsorbent for water treatment, offering significant advantages in adsorption efficiency, ease of regeneration, stability, and reduced environmental impacts. Its adoption across diverse wastewater treatment settings could substantially enhance the removal of NOM, enhance water quality management, and promote more sustainable treatment processes. Materials and methods Chemical reagents HA was purchased from Alfa Aesar (China) Chemical Co., Ltd. Methylene blue, Congo red, Rhodamin B, sodium hydroxide, and anhydrous ethanol were purchased from Sinopharm Chemical Reagent Co., Ltd. Oxytetracycline hydrochloride, sodium citrate, ammonia, hydrochloric acid, and hydrogen peroxide were purchased from Aladdin Reagent (Shanghai) Co., Ltd. Tetrabutyl titanate and polyethylene glycol 600 were purchased from Shanghai Lingfeng Reagent Co., Ltd. La(NO 3 ) 3 ·6H 2 O, Fe(NO 3 ) 3 ·9H 2 O, and Co(NO 3 ) 3 ·6H 2 O were purchased from Shanghai Macklin Biochemical Co., Ltd. The chemicals used in this investigation were of analytical grade and no additional purification steps were conducted on any of the reagents. All solutions were prepared using deionized water (DI). Synthesis of LFTCO adsorbents LaFeO 3 (LFO) and LaFe 0.55 Co 0.45 O 3 (LFCO) perovskite oxides were synthesized using a sol-gel method followed by calcination. First, the metal compounds of La(NO 3 ) 3 ·6H 2 O, Fe(NO 3 ) 3 ·9H 2 O, and Co(NO 3 ) 2 ·6H 2 O were mixed, stirred, and dissolved in a beaker. The molar ratio was La: Fe = 1:1 for preparing LFO and La: Fe: Co = 1:0.55:0.45 for preparing LFCO. Sodium citrate was added to the mixed metal solution to achieve a molar ratio of 1:5 between metal cations and citrate anions. The pH of the metal solution was adjusted to 4 using 20% ammonia solution. The mixed metal solution was stirred continuously at 80°C until it transformed into a sol-gel state. The resulting wet gel was placed in a preheated oven and dried at 120°C overnight. The dried gel was then placed in a muffle furnace and heated from 20°C to 300°C at a rate of 5°C/min. It was then held at 300°C for 3 h before being heated further to the final temperature of 700°C, where it was held for 5 h. After natural cooling of the muffle furnace, the desired product (LFO and LFCO) was obtained. LaFe 0.55 Ti 0.45 O 3 (LFTO) and LaFe 0.55 Co 0.45−x Ti x O 3 (LFTCO) were synthesized by adding titanium dioxide sol to the above mixed metal solution. Titanium dioxide sol was prepared by adding tetrabutyl titanate, anhydrous ethanol, PEG600, and deionized water in a molar ratio of 3:12:3:1 to form a transparent sol. The prepared Ti dioxide sol was slowly added into the mixed metal solution and stirred sufficiently for 1 hour at 50°C. The molar ratio was La:Fe:Ti = 1:0.55:0.45 for preparing LFTO. For the preparation of dual-doped LaFe 0.55 Co 0.45−x Ti x O 3 (LFTCO, x = 0.1, 0.2, 0.3, and 0.4), the molar ratio is La:Fe:Co:Ti = 1:0.55:0.45-x:x. For example, the preparation of dual-doped LFTCO-0.3, the corresponding molar ratio is La:Fe:Co:Ti = 1:0.55:0.15:0.3. Sodium citrate and ammonia solution were then added sequentially to the mixed metal solution in the same steps as above. The mixed metal solution was stirred continuously at 80°C until it transformed into a sol-gel state. The perovskite oxide-type adsorbent, LFTO and LFTCO were subsequently obtained using the same dry and annealing conditions. Material characterizations The surface morphology of metal oxide was characterized by scanning electron microscopy (SEM, HITACHI S-4800, Japan). The elemental composition of metal oxide was obtained by energy-dispersive X-ray spectroscopy (EDX, Horiba, Japan). The morphological structure was further analyzed by transmission electron microscopy (TEM, FEI Tecnai F20, USA). The crystal morphology of the perovskite oxide-type adsorbents was analyzed by X-ray diffraction spectroscopy (XRD, RIGAKU MiniFlex600, Japan). The functional groups of perovskite oxide-type adsorbents were identified by Fourier transform infrared spectroscopy (FT-IR, Thermo Nicolet8700, USA). The textural properties of the perovskite oxide-type adsorbents were assessed by N 2 adsorption/desorption analysis (BET, Micromeritics ASAP 2460, USA). Metal cation states and oxygen forms were investigated by X-ray photoelectron spectrometry (XPS, ESCALAB 250XI, USA). Ferromagnetism was measured using a vibrating sample magnetometer (VSM, Quantum Design Dyna Cool, USA) at room temperature. The zeta potential of perovskite oxide-type adsorbents in aqueous solution was determined by laser scattering method (Malvern Nano ZS90, UK). Additionally, the absorbance of HA at 254 nm was determined by UV-visible spectrophotometry (Perkin Elmer Lambda950, USA). The dissolution concentrations of leached metal ions were measured by inductively coupled plasma spectrometry (ICP, Optima 7000DV, USA). The hydrophilicity and water distribution characteristics of the adsorbents were characterized by low-field nuclear magnetic resonance spectroscopy (LF-NMR, NM42-40H-I, Suzhou Niumag). Computational simulation Density Functional Theory (DFT) calculations were performed on the small molecules, lanthanum ferrate crystals, and their doped variants involved in the experiments. The details are described in the Supplementary Text. Declarations Acknowledgements This work was financially supported by the National Natural Science Foundation of China (21921006, 22208147, 22250410273, 22478177), Jiangsu Provincial Department of Science and Technology (BK20232010), and Jiangsu Provincial Key Research and Development Project (BE2023058). 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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-5225322","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":374449552,"identity":"88d29c06-6647-47c4-975c-e1a0193da916","order_by":0,"name":"Ze-Xian Low","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAABCklEQVRIie3RMUsDMRTA8RcC75azWXMc+Blel5Yi9b7KFcEuVpyKoNSDQlzaPeAXcTwJnMtZ14IOnTrfaAfB3CnicPY6Fpo/JCSQHwkEwOXaxzggwJVdeHYU5QZ8O7CJULUApgFlM4E/hNvDzaTr8fWqoNMIOM/C/mNrIryXFIqxAfGQ1JLeFLttTWeDhON5OMpRBrPLmOmFAfme1hIyPoY+8di+qvM2UihpabdHygDJeBu5iyrSsyQqyWczMSwpCStvkZawrQQ7gabngeI43MwVBjq/oKfZYujL5T/k1axlcX0TCW9qaKMyIe7z9upjfHIsdD357ecjsmpO4ft3dup214Mul8t1QH0BLs5LJhodb7AAAAAASUVORK5CYII=","orcid":"https://orcid.org/0000-0002-3454-4044","institution":"Nanjing Tech University","correspondingAuthor":true,"prefix":"","firstName":"Ze-Xian","middleName":"","lastName":"Low","suffix":""},{"id":374449553,"identity":"7544cded-e1da-418c-bb22-5b69f99d1191","order_by":1,"name":"Lekai Zhao","email":"","orcid":"","institution":"Nanjing Tech University","correspondingAuthor":false,"prefix":"","firstName":"Lekai","middleName":"","lastName":"Zhao","suffix":""},{"id":374449554,"identity":"7840f66f-4768-4820-be58-407881509987","order_by":2,"name":"Shuang Han","email":"","orcid":"","institution":"Nanjing Tech University","correspondingAuthor":false,"prefix":"","firstName":"Shuang","middleName":"","lastName":"Han","suffix":""},{"id":374449555,"identity":"63d88342-6fe9-41ad-a334-0d82013a7bdd","order_by":3,"name":"Xiao Ma","email":"","orcid":"","institution":"Nanjing Tech University","correspondingAuthor":false,"prefix":"","firstName":"Xiao","middleName":"","lastName":"Ma","suffix":""},{"id":374449556,"identity":"ba5d2525-245a-4b6e-81e6-fecc68b5b88c","order_by":4,"name":"Ming Zhou","email":"","orcid":"","institution":"Nanjing Tech University","correspondingAuthor":false,"prefix":"","firstName":"Ming","middleName":"","lastName":"Zhou","suffix":""},{"id":374449557,"identity":"c15133e5-60dc-41f1-a6c7-83aaf0c965ca","order_by":5,"name":"Qiuyue Wang","email":"","orcid":"","institution":"Nanjing Tech University","correspondingAuthor":false,"prefix":"","firstName":"Qiuyue","middleName":"","lastName":"Wang","suffix":""},{"id":374449558,"identity":"1af3c56e-1ec8-4a62-a390-d14316c2f1d7","order_by":6,"name":"Shasha Feng","email":"","orcid":"","institution":"Nanjing Tech University","correspondingAuthor":false,"prefix":"","firstName":"Shasha","middleName":"","lastName":"Feng","suffix":""},{"id":374449559,"identity":"26c2bfdd-5d08-41b8-b163-53e169970f5a","order_by":7,"name":"Zhaoxiang Zhong","email":"","orcid":"","institution":"Nanjing Tech University","correspondingAuthor":false,"prefix":"","firstName":"Zhaoxiang","middleName":"","lastName":"Zhong","suffix":""},{"id":374449560,"identity":"c0318b49-db27-4237-871e-f2d09c78b724","order_by":8,"name":"Weihong Xing","email":"","orcid":"","institution":"Nanjing Tech University","correspondingAuthor":false,"prefix":"","firstName":"Weihong","middleName":"","lastName":"Xing","suffix":""}],"badges":[],"createdAt":"2024-10-08 12:30:14","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-5225322/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-5225322/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1038/s41467-026-70286-6","type":"published","date":"2026-03-12T04:00:00+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":71142657,"identity":"ff87c1b2-0998-4234-b2e5-676be89ac489","added_by":"auto","created_at":"2024-12-11 13:58:59","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":4293261,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003ePhysicochemical and structural characterization of adsorbents.\u003c/strong\u003e \u003cstrong\u003ea,\u003c/strong\u003e LFCTO crystal configuration. \u003cstrong\u003eb,\u003c/strong\u003e TEM. \u003cstrong\u003ec,\u003c/strong\u003e High-resolution TEM. \u003cstrong\u003ed,\u003c/strong\u003e SAED pattern of LFCTO-0.3. \u003cstrong\u003ee,\u003c/strong\u003e XRD patterns. \u003cstrong\u003ef,\u003c/strong\u003e Variation in the most intense peak (110). \u003cstrong\u003eg,\u003c/strong\u003e FTIR spectra. \u003cstrong\u003eh,\u003c/strong\u003e Ferromagnetism property (M-H curves) of LFCTO. The spin density viewed from the side and top of \u003cstrong\u003ei \u003c/strong\u003eand\u003cstrong\u003e l,\u003c/strong\u003e the pristine LaFeO\u003csub\u003e3\u003c/sub\u003e crystals, \u003cstrong\u003ej \u003c/strong\u003eand\u003cstrong\u003e m,\u003c/strong\u003e Co-doped LaFeO\u003csub\u003e3\u003c/sub\u003e crystals and \u003cstrong\u003ek \u003c/strong\u003eand\u003cstrong\u003e n,\u003c/strong\u003e Ti-doped LaFeO\u003csub\u003e3\u003c/sub\u003e crystals.\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-5225322/v1/e5926069c9fa9bce017d91ed.png"},{"id":71142664,"identity":"76a72414-8677-430d-a479-21ec0ac2c9ce","added_by":"auto","created_at":"2024-12-11 13:58:59","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":1054287,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eMicrostructure and metal ion state analysis of adsorbents.\u003c/strong\u003e \u003cstrong\u003ea,\u003c/strong\u003e BET analysis and \u003cstrong\u003eb,\u003c/strong\u003e pore size distribution of LFCTO. XPS analysis of \u003cstrong\u003ec,\u003c/strong\u003e survey, \u003cstrong\u003ed,\u003c/strong\u003e Fe 2p, \u003cstrong\u003ee,\u003c/strong\u003eCo 2p and \u003cstrong\u003ef, \u003c/strong\u003eO 1s of LFCTO-0.3 and LFO.\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-5225322/v1/747d173eb7fdff962a76d63a.png"},{"id":71143292,"identity":"bff55dd2-3a0b-4586-8e75-481381db8265","added_by":"auto","created_at":"2024-12-11 14:06:59","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":3470895,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eHA adsorption performance and mechanistic analysis.\u003c/strong\u003e Adsorption performance of LFCTO-0.3: The effect of \u003cstrong\u003ea,\u003c/strong\u003e HA concentration, \u003cstrong\u003eb,\u003c/strong\u003e the amount of adsorbent and \u003cstrong\u003ec, \u003c/strong\u003epH, adsorption conditions: pH = 7 , HA concentration = 30 mg/L, amount of adsorbent = 0.2 g/L, time = 80 min, except for the specific varied parameter. \u003cstrong\u003ed,\u003c/strong\u003e The zeta potential of LFCTO-0.3 and HA. Adsorption kinetics of LFCTO-0.3 to HA using \u003cstrong\u003ee,\u003c/strong\u003e PSO model fitting to static adsorption capacity (\u003cem\u003eq\u003c/em\u003e\u003csub\u003e\u003cem\u003et\u003c/em\u003e\u003c/sub\u003e) at different concentrations (10 ~ 300 mg/L). \u003cstrong\u003ef,\u003c/strong\u003e The experimental adsorption capacity of LFCTO-0.3 to HA fitting with Langmuir isotherm and Freundlich isotherm for HA adsorption on LFCTO-0.3. The electrostatic potential of \u003cstrong\u003eg,\u003c/strong\u003e HA (different protonated status, aqueous environment). \u003cstrong\u003eh,\u003c/strong\u003e Thermodynamic for HA adsorption on LFCTO-0.3. \u003cstrong\u003ei,\u003c/strong\u003e LF-NMR spectra of LFO and LFCTO-0.3 using water as probe molecule, and schematic illustration of spaces of I-sub-nanometer confinement region, II-nanoconfinement region, and III-free water. Independent gradient model based on Hirshfeld partition (IGMH) analysis of weak interactions within HA-LaFeO\u003csub\u003e3\u003c/sub\u003e and its doped systems. \u003cstrong\u003ej,\u003c/strong\u003e HA-LaFeO\u003csub\u003e3\u003c/sub\u003e system; \u003cstrong\u003ek,\u003c/strong\u003e HA-Co doped LaFeO\u003csub\u003e3\u003c/sub\u003e system; \u003cstrong\u003el, \u003c/strong\u003eHA-Ti doped LaFeO\u003csub\u003e3\u003c/sub\u003e system. In the diagrams, the red isosurfaces represent regions of attraction, while blue denotes repulsion areas, with their size and color intensity being directly proportional.\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-5225322/v1/1eb51238f614808717a2a941.png"},{"id":71144760,"identity":"c95b4bff-d660-4f6b-ae20-9fb39b60224f","added_by":"auto","created_at":"2024-12-11 14:14:59","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":1709611,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eDynamic adsorption and corresponding models under various conditions. a,\u003c/strong\u003e Flow chart of dynamic adsorption experiment. \u003cstrong\u003eb, \u003c/strong\u003eBDST analysis. The effect of \u003cstrong\u003ec, \u003c/strong\u003einfluent flow rate on dynamic adsorption of HA with analysis of \u003cstrong\u003eg,\u003c/strong\u003e Thomas and \u003cstrong\u003ek,\u003c/strong\u003eYoon-Nelson model. The effect of \u003cstrong\u003ed,\u003c/strong\u003e bed height on dynamic adsorption of HA with analysis of \u003cstrong\u003eh,\u003c/strong\u003e Thomas and \u003cstrong\u003el,\u003c/strong\u003e Yoon-Nelson model. The effect of \u003cstrong\u003ee,\u003c/strong\u003e feed concentration on dynamic adsorption of HA with analysis of \u003cstrong\u003ei, \u003c/strong\u003eThomas and \u003cstrong\u003em,\u003c/strong\u003e Yoon-Nelson model. The effect of \u003cstrong\u003ef,\u003c/strong\u003e feed pH on dynamic adsorption of HA with analysis of \u003cstrong\u003ej,\u003c/strong\u003e Thomas and \u003cstrong\u003en,\u003c/strong\u003eYoon-Nelson model. Adsorption conditions: inlet flow rate = 1.4mL /min, bed height = 2.4cm, feed concentration = 30mg /L, inlet flow rate = 1.4mL /min, pH = 7, except for the specific varied parameter.\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-5225322/v1/20d079bd235a46eacd8ca8a0.png"},{"id":71143294,"identity":"ac24a6c6-051f-4b78-8d2b-6a4a464cba8e","added_by":"auto","created_at":"2024-12-11 14:06:59","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":246295,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eCyclic performance and stability of perovskite oxide-type absorbent.\u003c/strong\u003e \u003cstrong\u003ea,\u003c/strong\u003e Static cycle step diagram. \u003cstrong\u003eb,\u003c/strong\u003e Static cyclic adsorption performance of LFCTO-0.3 \u003cstrong\u003ec,\u003c/strong\u003e Dynamic cycle step diagram. \u003cstrong\u003ed,\u003c/strong\u003e Dynamic cyclic adsorption-desorption experiments. \u003cstrong\u003ee,\u003c/strong\u003e Comparison of HA maximum adsorption capacity (\u003cem\u003eq\u003c/em\u003e\u003csub\u003e\u003cem\u003emax\u003c/em\u003e\u003c/sub\u003e) of LFCTO and the other adsorbents. The colors in e represent different regeneration methods: purple for calcination, blue for Fenton reaction, orange for solvent elution, and light blue for ultrasonication.\u003c/p\u003e","description":"","filename":"5.png","url":"https://assets-eu.researchsquare.com/files/rs-5225322/v1/83da93049239cd1b95e9ea91.png"},{"id":107973464,"identity":"0c002799-fb81-4a05-9aa9-fba78e2d4007","added_by":"auto","created_at":"2026-04-28 07:11:26","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":11247352,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-5225322/v1/18817b0e-d6a0-4861-b2ba-03f5bf84ccb1.pdf"},{"id":71142661,"identity":"6da25e51-c897-4b18-bc57-ca7791d2a65d","added_by":"auto","created_at":"2024-12-11 13:58:59","extension":"docx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":1187003,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cbr\u003e\u003c/p\u003e","description":"","filename":"SupportingInformation.docx","url":"https://assets-eu.researchsquare.com/files/rs-5225322/v1/7f750911b9ab28482085ef87.docx"},{"id":71142658,"identity":"732f5bbc-9b40-46f0-95f4-adef79b0bbe4","added_by":"auto","created_at":"2024-12-11 13:58:59","extension":"png","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":184967,"visible":true,"origin":"","legend":"","description":"","filename":"GraphicalAbstract.png","url":"https://assets-eu.researchsquare.com/files/rs-5225322/v1/de9e31b960dad4756057465d.png"}],"financialInterests":"There is \u003cb\u003eNO\u003c/b\u003e Competing Interest.","formattedTitle":"Dual-Metal-Doped Perovskite Adsorbents for Efficient Removal of Humic Acid","fulltext":[{"header":"Introduction","content":"\u003cp\u003eWith the expanding global population and diminishing freshwater resources, developing advanced wastewater treatment and reuse technologies has become critically important for sustaining water availability\u003csup\u003e\u003cspan additionalcitationids=\"CR2\" citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e\u003c/sup\u003e. Among the water contaminants, humic acid (HA)\u0026mdash;formed from the decay of plant and animal matter\u0026mdash;significantly contributes to natural organic matter (NOM) in freshwater\u003csup\u003e\u003cspan additionalcitationids=\"CR5 CR6 CR7\" citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e\u003c/sup\u003e. HA is a high molecular weight organic substance with a complex and stable structure that is refractory and resists biodegradation under natural conditions\u003csup\u003e\u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e,\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e\u003c/sup\u003e. If left untreated, HA in water supplies can form stable complexes with heavy metal ions, enhancing their persistence and mobility, which leads to the accumulation of pollutants in sediments and organisms\u003csup\u003e\u003cspan additionalcitationids=\"CR12 CR13 CR14 CR15\" citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e\u003c/sup\u003e. Furthermore, during chlorination, HA can form carcinogenic, teratogenic, and mutagenic disinfection byproducts such as trihalomethanes and haloacetic acids, severely compromising water quality and human health\u003csup\u003e\u003cspan additionalcitationids=\"CR18 CR19 CR20 CR21\" citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e\u003c/sup\u003e. Hence, the effective removal of HA during wastewater treatment processes is crucial for ensuring safe and clean water. Currently, three main approaches exist for HA removal: biological methods (e.g., biological treatment\u003csup\u003e\u003cspan additionalcitationids=\"CR24\" citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e\u003c/sup\u003e), chemical methods (e.g., electrolysis\u003csup\u003e\u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e\u003c/sup\u003e, flocculation/coagulation\u003csup\u003e27\u003c/sup\u003e, and catalytic oxidation\u003csup\u003e\u003cspan additionalcitationids=\"CR29\" citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e\u003c/sup\u003e), and physical methods (e.g., membrane filtration\u003csup\u003e\u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e31\u003c/span\u003e,\u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e\u003c/sup\u003e and adsorption\u003csup\u003e\u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e,\u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e\u003c/sup\u003e). Among these, adsorption is widely employed due to its cost-effective, simple design, operation ease, environmental friendliness, and high efficiency\u003csup\u003e\u003cspan citationid=\"CR35\" class=\"CitationRef\"\u003e35\u003c/span\u003e\u003c/sup\u003e. However, traditional adsorbents such as resins and activated carbon are limited by their low adsorption capacity, low specific surface area, and poor regeneration properties\u003csup\u003e\u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e36\u003c/span\u003e,\u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e37\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003ePerovskite oxides, represented by the formula ABO\u003csub\u003e3\u003c/sub\u003e, are a diverse family of mixed metal oxides renowned for their highly tunable compositions and physicochemical properties, making them suitable for a wide range of applications, including solar cells\u003csup\u003e\u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e38\u003c/span\u003e,\u003cspan citationid=\"CR39\" class=\"CitationRef\"\u003e39\u003c/span\u003e\u003c/sup\u003e, fuel cells\u003csup\u003e\u003cspan citationid=\"CR40\" class=\"CitationRef\"\u003e40\u003c/span\u003e,\u003cspan citationid=\"CR41\" class=\"CitationRef\"\u003e41\u003c/span\u003e\u003c/sup\u003e, electromagnetic materials\u003csup\u003e\u003cspan additionalcitationids=\"CR43\" citationid=\"CR42\" class=\"CitationRef\"\u003e42\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR44\" class=\"CitationRef\"\u003e44\u003c/span\u003e\u003c/sup\u003e, chemical sensors\u003csup\u003e\u003cspan citationid=\"CR45\" class=\"CitationRef\"\u003e45\u003c/span\u003e\u003c/sup\u003e, and catalysts\u003csup\u003e\u003cspan citationid=\"CR46\" class=\"CitationRef\"\u003e46\u003c/span\u003e, \u003cspan citationid=\"CR47\" class=\"CitationRef\"\u003e47\u003c/span\u003e\u003c/sup\u003e. In these crystalline structure, A-site elements\u0026mdash;typically rare earth metals or alkaline earth metals (e.g., La, Pr, Gd) characterized by larger ionic radii\u0026mdash;occupy the central position of the cubic lattice, while B-site elements\u0026mdash;usually transition metals (e.g., Ti, Mn, Fe, Co, Cr) with smaller ionic radii\u0026mdash;occupy corner-sharing octahedra\u003csup\u003e\u003cspan citationid=\"CR48\" class=\"CitationRef\"\u003e48\u003c/span\u003e\u003c/sup\u003e. A distinguishing feature of perovskite oxides is their unique structural tunability and design flexibility, which allows for the customization and enhancement of specific properties\u003csup\u003e\u003cspan citationid=\"CR49\" class=\"CitationRef\"\u003e49\u003c/span\u003e\u003c/sup\u003e. For instance, Ti doping in LaFeO\u003csub\u003e3\u003c/sub\u003e perovskites via a sol-gel method, enhances catalytic activity, resulting in improved removal and mineralization rates of chlorophenols\u003csup\u003e\u003cspan citationid=\"CR50\" class=\"CitationRef\"\u003e50\u003c/span\u003e\u003c/sup\u003e. Ti doping also augments magnetic properties by influencing the Fe spin through the unpaired electrons of Ti\u003csup\u003e3+\u003c/sup\u003e ions\u003csup\u003e51\u003c/sup\u003e. Similarly, Co doping introduces abundant active sites that accelerate methane activation, while Sr doping increases oxygen vacancies, facilitating the migration of oxygen anions for enhanced reactivity and resistance to coking\u003csup\u003e\u003cspan citationid=\"CR52\" class=\"CitationRef\"\u003e52\u003c/span\u003e\u003c/sup\u003e. Transition metal doping at the B site can create electron-deficient states, leading to the formation of oxygen vacancies. Specifically, dual doping exploits complementary effects between metal ions of differing ionic radii, simultaneously enhancing multiple properties and improving material stability for extended use\u003csup\u003e\u003cspan citationid=\"CR53\" class=\"CitationRef\"\u003e53\u003c/span\u003e,\u003cspan citationid=\"CR54\" class=\"CitationRef\"\u003e54\u003c/span\u003e\u003c/sup\u003e. We hypothesize that targeted doping strategies can tailor perovskite materials into high-performance adsorbents with enhanced adsorption capacities and regenerative functionalities essential for efficient and sustainable wastewater treatment processes.\u003c/p\u003e \u003cp\u003eHere we present a dual-doping strategy for the fabrication of perovskite-type adsorbent aimed at effectively remediating HA-contaminated water. By simultaneously doping Ti and Co at the B-site of LaFeO\u003csub\u003e3\u003c/sub\u003e, we developed an adsorbent (LFTCO) that demonstrates rapid and enhanced HA adsorption, as confirmed through dynamic adsorption studies and mechanistic modeling. We further demonstrate that this Fenton-active adsorbent can be regenerated \u003cem\u003ein situ\u003c/em\u003e as part of a continuous process or magnetically recovered for subsequent chemical regeneration. The LFTCO adsorbents exhibited excellent performance stability for HA adsorption and chemical regeneration over 280 hours in a continuous adsorption-regeneration cycle, all while maintaining their crystalline structure. This unique stability enables an energy-efficient, one-step regeneration process, setting it apart from traditional methods that require high-temperature calcination or solvent elution.\u003c/p\u003e"},{"header":"Results and discussion","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003eFabrication of LFTCO absorbents\u003c/h2\u003e \u003cp\u003eAs a typical ABO\u003csub\u003e3\u003c/sub\u003e-type perovskite oxide, LaFeO\u003csub\u003e3\u003c/sub\u003e has an atomic ratio of approximately 1:1:3 for La, Fe, and O\u003csup\u003e\u003cspan citationid=\"CR55\" class=\"CitationRef\"\u003e55\u003c/span\u003e,\u003cspan citationid=\"CR56\" class=\"CitationRef\"\u003e56\u003c/span\u003e\u003c/sup\u003e. In the case of dual-doped LFTCO, La occupies the A-site, while Fe, Co, and Ti occupy the B-site (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ea). The LF\u003csub\u003e0.55\u003c/sub\u003eT\u003csub\u003ex\u003c/sub\u003eC\u003csub\u003e0.45\u0026minus;x\u003c/sub\u003eO (x\u0026thinsp;=\u0026thinsp;0.1, 0.2, 0.3, and 0.4) oxides were successfully synthesized using a facile sol-gel method. The resulting perovskite oxide-type adsorbents exhibited uniform block-like porous structure (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eb, Supplementary Fig. S2a-d) and the HRTEM image (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ec) depicted lattice fringes of 0.28 nm, corresponding to the (110) plane of LaFeO\u003csub\u003e3\u003c/sub\u003e. Elemental composition analysis using energy dispersive X-ray spectroscopy (Supplementary Fig. S2e) confirmed an atomic ratio of La: (Fe\u0026thinsp;+\u0026thinsp;Ti\u0026thinsp;+\u0026thinsp;Co): O was approximately 1:1:3, verifying the successful synthesis of LFTCO via the sol-gel method. X-ray diffraction spectroscopy (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ee) revealed that the diffraction peaks of LFTCO closely matched the characteristic peaks of LaFeO\u003csub\u003e3\u003c/sub\u003e (JCPDS no. 75\u0026ndash;0541), consistent with its crystal structure, which was also confirmed by the selected area electron diffraction (SAED) pattern (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ed)\u003csup\u003e\u003cspan citationid=\"CR57\" class=\"CitationRef\"\u003e57\u003c/span\u003e,\u003cspan citationid=\"CR58\" class=\"CitationRef\"\u003e58\u003c/span\u003e\u003c/sup\u003e. Analysis of the (110) crystal plane (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ef) showed that as the Ti doping ratio increased, there was an overall left shift in the diffraction peaks, indicating an increase in crystal plane spacing\u003csup\u003e\u003cspan citationid=\"CR59\" class=\"CitationRef\"\u003e59\u003c/span\u003e\u003c/sup\u003e. Interestingly, at a doping ratio of x\u0026thinsp;=\u0026thinsp;0.3, the diffraction peak shifted to its original position, maintaining the original configuration of LeFeO\u003csub\u003e3\u003c/sub\u003e. This shifting phenomenon, attributed to changes in the metal-oxygen bond lengths induced by doping, suggest that Ti/Co double doping can stabilize the perovskite crystal configuration. FTIR spectroscopy (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eg) revealed peaks at approximately 576 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, indicating the presence of metal oxide bonds, specifically attributed to the Fe-O stretching vibration characteristic of the octahedral FeO\u003csub\u003e6\u003c/sub\u003e group in LaFeO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e60\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eMost adsorbents are difficult to separate from wastewater streams, which poses challenges for their reuse. Consequently, the magnetic separation of suspended adsorbents has been extensively researched\u003csup\u003e\u003cspan citationid=\"CR61\" class=\"CitationRef\"\u003e61\u003c/span\u003e\u003c/sup\u003e. The ferromagnetic properties of the synthesized perovskite oxides was evaluated using M-H curves, as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eh and Supplementary Table \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003e with the saturation magnetization measured as the primary indicator of their recovery capability\u003csup\u003e\u003cspan citationid=\"CR62\" class=\"CitationRef\"\u003e62\u003c/span\u003e\u003c/sup\u003e. As the Ti doping ratio increased, the magnetization initially increased and then decreased. In LFTCO, Ti can exchange-couple with Fe, shifting the Fe spin moment, which facilitates small-angle rotation tilt, thereby enhancing overall ferromagnetism due to uncompensated Fe spins. Surface oxygen vacancies disturb the antiparallel spin ordering in Fe\u003csup\u003e3+\u003c/sup\u003e-O-Fe\u003csup\u003e3+\u003c/sup\u003e and Fe\u003csup\u003e4+\u003c/sup\u003e-O\u003csup\u003e2\u003c/sup\u003e-Fe\u003csup\u003e4+\u003c/sup\u003e through super-exchange interactions, leading to increased magnetization. As the Fe spin moment increases, the presence of uncompensated spins allows free motion of the domain walls, further enhancing magnetization. However, high concentrations of nonmagnetic Ti can inhibit domain wall motion, resulting in decreased magnetization\u003csup\u003e\u003cspan citationid=\"CR63\" class=\"CitationRef\"\u003e63\u003c/span\u003e\u003c/sup\u003e. The results indicated that LFTCO-0.3 and LFTCO-0.2 exhibited strong ferromagnetic behavior (Ms\u0026thinsp;=\u0026thinsp;7.36 emu/g and 5.24 emu/g, respectively), which is advantageous for recycling and utilization in water treatment processes\u003csup\u003e\u003cspan citationid=\"CR64\" class=\"CitationRef\"\u003e64\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eTo further elucidate the effect of Ti/Co doping on the magnetic properties of the materials, we performed theoretical validation using Density Functional Theory (DFT) calculations. LaFeO\u003csub\u003e3\u003c/sub\u003e is a G-type antiferromagnetic crystal, and its weak magnetism observed experimentally has been attributed to Oxygen vacancies introduced during synthesis (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ei, l). Pristine LaFeO\u003csub\u003e3\u003c/sub\u003e crystals lack unpaired electrons, resulting in zero spin density throughout the crystal lattice, and are thus non-ferromagnetic. Introducing Co dopants significantly alters the electronic structure of the closed-shell LaFeO\u003csub\u003e3\u003c/sub\u003e crystal. This is due to the electronic configuration of Co (III), which is [Ar]4s\u003csup\u003e0\u003c/sup\u003e3d\u003csup\u003e\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e\u003c/sup\u003e. According to Hund's rule, the 3d orbitals of Co(III) have four unpaired electrons, leading to a net magnetic moment. The difference in the number of unpaired electrons compared to Fe(III) disrupts the originally stable G-type antiferromagnetic structure when Co is incorporated into the lattice. Figure\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ej, m show that Co-doped LaFeO\u003csub\u003e3\u003c/sub\u003e crystals exhibit prevalent spin density, indicating the potential to become paramagnetic or ferromagnetic materials. Conversely, higher doping levels of Ti reduces the magnetism of the system because the electronic configuration of Ti (III) is [Ar]4s\u003csup\u003e0\u003c/sup\u003e3d\u003csup\u003e\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e, with only one unpaired electron in the 3d orbital. This results in a system with fewer unpaired electrons, leading to non-magnetism or weak ferromagnetism. Figure\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ek, n further confirm this, showing only one unpaired electron present in the system.\u003c/p\u003e \u003c/div\u003e\n\u003ch3\u003eMicrostructure and metal ion state analysis of LFTCO absorbents\u003c/h3\u003e\n\u003cp\u003eThe specific surface areas and pore size distributions of LFTCO, which influence its adsorption capacity and rate, were determined by N\u003csub\u003e2\u003c/sub\u003e sorption porosimetry. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ea, the N\u003csub\u003e2\u003c/sub\u003e adsorption/desorption isotherms of LFTCO exhibited typical type IV curves with hysteresis between P/P\u003csub\u003e0\u003c/sub\u003e\u0026thinsp;=\u0026thinsp;0.5 and 1.0, indicating a mesoporous structure\u003csup\u003e\u003cspan citationid=\"CR65\" class=\"CitationRef\"\u003e65\u003c/span\u003e\u003c/sup\u003e. The pore size distribution (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eb) revealed that LFTCO had pore size ranging from 2 to 30 nm, with LFTCO-0.3 possessing the smallest pore size among them. These results indicate that LFTCO-0.3 had the largest specific surface area. Further analysis of pore volume showed that LFTCO-0.3 had the highest total pore volume of 0.040 cm\u003csup\u003e3\u003c/sup\u003e\u0026middot;g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e (Supplementary Table \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003e). This suggests that LFTCO-0.3 could exhibit enhanced adsorption compared to other LFTCO samples.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eWe performed XPS to determine the surface chemical composition and chemical states of LFO and LFTCO-0.3 (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ec-f). The XPS survey spectra (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ec) confirm that Ti and Co are successfully doped into the LFTCO-0.3 lattice. The A-site La element, which stabilizes the crystal structure, is present as La\u003csup\u003e3+\u003c/sup\u003e (Supplementary Fig. S3a). The characteristic peaks of Ti 2p at 458.1 eV and 463.8 eV correspond to Ti 2p\u003csub\u003e3/2\u003c/sub\u003e and Ti 2p\u003csub\u003e1/2\u003c/sub\u003e of Ti\u003csup\u003e4+\u003c/sup\u003e, respectively (Supplementary Fig. S3b). Compared to LFO, the Fe\u003csup\u003e2+\u003c/sup\u003e/Fe\u003csup\u003e3+\u003c/sup\u003e ratio increases (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ed), and the redox dynamics between Fe\u003csup\u003e2+\u003c/sup\u003e/Fe\u003csup\u003e3+\u003c/sup\u003e and Co\u003csup\u003e2+\u003c/sup\u003e/Co\u003csup\u003e3+\u003c/sup\u003e promote the generation of surface oxygen vacancies to maintain charge neutrality. This is further confirmed by the O 1s XPS spectrum (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ef), where peaks below 530 eV correspond to lattice oxygen and peaks above 530 eV correspond to chemisorbed oxygen\u003csup\u003e\u003cspan citationid=\"CR66\" class=\"CitationRef\"\u003e66\u003c/span\u003e\u003c/sup\u003e. Compared to LFO, the increased ratio of lattice oxygen to chemisorbed oxygen in LFTCO-0.3 indicates that Ti/Co doping promotes the creation of more oxygen vacancies in the LFO lattice, thus improving the adsorption performance of the material\u003csup\u003e\u003cspan citationid=\"CR67\" class=\"CitationRef\"\u003e67\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e\n\u003ch3\u003eStatic HA adsorption on LFTCO adsorbent\u003c/h3\u003e\n\u003cp\u003eUsing HA as the target contaminant, Supplementary Fig. S4 illustrates the differences in adsorption performance among various adsorbents: unmodified (LFO), single-doped (LFTO and LFCO), and dual-doped (LFTCO). The removal rates of HA in water revealed that adsorption efficiency improved with the doping of Ti and Co metals, with the dual-doped LFTCO demonstrating the most significant effect. Among these, LFTCO-0.3 exhibited the highest adsorption performance. This improvement is attributed to dual doping at the B sites, which effectively enhances the specific surface area, increases the number of adsorption sites for pollutant molecules, and promotes the formation of oxygen vacancies on the surface of lanthanum ferrite. These oxygen vacancies enhance electron mobility and chemical activity, further boosting adsorption. Consequently, LFTCO-0.3 was selected for subsequent experiments.\u003c/p\u003e \u003cp\u003eAdsorption experiments were carried out with different concentrations of HA (\u003cem\u003eC\u003c/em\u003e\u003csub\u003e\u003cem\u003eHA\u003c/em\u003e\u003c/sub\u003e = 10, 30, and 50 mg/L) at a fixed adsorbent dosage (\u003cem\u003eC\u003c/em\u003e\u003csub\u003e\u003cem\u003eads\u003c/em\u003e\u003c/sub\u003e = 0.2 g/L) and pH\u0026thinsp;=\u0026thinsp;7 to compare the removal efficiency and adsorption capacity, aiming to identify the dual-doped perovskite oxide adsorbent with optimal performance (Supplementary Text S2). The results showed that all dual-doped LFTCO samples exhibited excellent adsorption for HA. Notably, LFTCO-0.3 demonstrated higher removal efficiency across different concentrations compared to other doping ratios (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ea), likely due to its largest specific surface area and smallest pore size among all dual-doped modified adsorbents (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eb and Supplementary Table \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003e). As the HA concentration increased, the adsorption sites were more fully utilized, further enhancing the adsorption effect. When the concentration of HA increased from 10 to 30 mg/L, the adsorption capacity of LFTCO-0.3 increased significantly. However, as the HA concentration was increased to 50 mg/L, the increase in adsorption capacity became less pronounced (Supplementary Fig. S5). Therefore, for subsequent experiments exploring varying conditions, an HA concentration of 30 mg/L was selected.\u003c/p\u003e \u003cp\u003eThe amount of adsorbent is a critical factor affecting adsorption performance. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003eb, the HA removal efficiency by LFTCO-0.3 increased with an increase in adsorbent dosage. When the adsorbent dosage was raised from 0.1 g/L to 0.2 g/L, the removal efficiency of HA significantly increased from 82\u0026ndash;97%. However, further increasing the dosage to 0.4 g/L only marginally increased the removal efficiency to 99%. This plateau is attributed to adsorbent aggregation at higher dosages, which reduces the accessible surface area and decreases the total number of active adsorption sites. Additionally, the limited number of HA molecules relative to the increased adsorbent restricts further improvements in removal efficiency. Meanwhile, the adsorption capacity gradually decreased as the adsorbent dosage increased from 0.1 to 0.4 g/L. This reduction is due to the presence of unsaturated adsorption sites at higher dosages, leading to a decrease in per-unit adsorption capacity. Considering both the removal efficiency and adsorption capacity, 0.2 g/L was selected as the optimal adsorbent dosage.\u003c/p\u003e \u003cp\u003eTo optimize the adsorption process for a wide range of real-world wastewater conditions, the effect of pH on adsorption was investigated (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ec). The adsorption performance of LFTCO-0.3 under various acidic and alkaline conditions is influenced by three primary factors: the surface charge of the adsorbent, the solubility of HA, and changes in HA molecular configuration\u003csup\u003e\u003cspan citationid=\"CR68\" class=\"CitationRef\"\u003e68\u003c/span\u003e,\u003cspan citationid=\"CR69\" class=\"CitationRef\"\u003e69\u003c/span\u003e\u003c/sup\u003e. The results indicated that the removal performance of HA by LFTCO-0.3 gradually increased as the solution pH ranged from 3 to 7. Under acidic conditions, HA molecules tend to polymerize and often exist as undissociated molecules or weakly ionic species, resulting in lower solubility. This enhances the interaction between HA and the adsorption sites on LFTCO-0.3, thereby improving the adsorption performance. Combined with the Zeta potential measurements (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ed), it was found that LFTCO-0.3 forms electrostatic attractions with negatively charged anions (HA\u0026thinsp;+\u0026thinsp;H\u003csub\u003e2\u003c/sub\u003eO\u0026rarr;H\u003csub\u003e3\u003c/sub\u003eO\u003csup\u003e+\u003c/sup\u003e+A\u003csup\u003e\u0026minus;\u003c/sup\u003e), promoting adsorption under acidic conditions\u003csup\u003e\u003cspan citationid=\"CR70\" class=\"CitationRef\"\u003e70\u003c/span\u003e,\u003cspan citationid=\"CR71\" class=\"CitationRef\"\u003e71\u003c/span\u003e\u003c/sup\u003e. As the pH increased from 7 to 11, the removal efficiency of HA by LFTCO-0.3 gradually decreased. This reduction is primarily due to electrostatic repulsion between the negatively charged adsorbent surface and HA molecules under alkaline conditions. Additionally, the increased solubility of HA in alkaline solutions further diminishes the adsorption capacity of LFTCO-0.3\u003csup\u003e72\u003c/sup\u003e. Hence, LFTCO-0.3 demonstrated notably effective adsorption performance for HA under both acidic and neutral conditions. Considering that the pH of HA solutions is generally around 7, the highest adsorption performance of LFTCO-0.3 at pH 7 indicates that highly efficient removal of HA can be achieved without the need for pH adjustment.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e\n\u003ch3\u003eElectrostatic modulation and thermodynamic insights into HA adsorption mechanisms\u003c/h3\u003e\n\u003cp\u003eTo investigate the enhanced adsorption and reaction mechanisms between HA and LFTCO-0.3, quantum chemical calculations were performed on HA molecules (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003eg). The results revealed significant differences in the electrostatic potential properties of HA molecules under various protonation states, corresponding to different pH conditions. At lower pH levels, both carboxyl groups of the HA molecule are protonated and electrically neutral. The electrostatic potential projection on its van der Waals surface shows a maximum surface electrostatic potential is 61.934 kcal/mol and a minimum of -39.613 kcal/mol, indicating significant polarization. The negatively charged regions are located near the carboxyl and nitro groups, while the positively charged regions are near the saturated cycloalkane structures. As the ambient pH increases, the HA molecule undergoes further ionization. At least one of the carboxyl groups becomes deprotonated, imparting a negative charge to the molecule. The van der Waals surface potentials becomes entirely negative, with the highest value decreasing to -5.270 kcal/mol and the lowest to -148.126 kcal/mol. With a further decrease in ambient proton concentration, the maximum electrostatic potential shifts to -39.613 kcal/mol. If the ambient proton concentration is reduced even further, all active hydrogens on the HA molecules dissociate, significantly enhancing the molecule's negative charge. The van der Waals surface then exhibits strong negative potential, with the highest being \u0026minus;\u0026thinsp;80.309 kcal/mol and the lowest \u0026minus;\u0026thinsp;242.539 kcal/mol. These calculations indicate that HA molecules tend to adsorb onto positively charged sites of the adsorbents due to electrostatic interactions. Consistent with the zeta potential test results, the increase in pH leads to HA molecules becoming more electronegative. Thus, as pH increases from 3 to 7, the enhanced negative charge of HA strengthens the electrostatic attraction with the positively charged surface of LFTCO-0.3, enhancing their removal from water. However, as the pH continues to increase beyond 7, the removal efficiency significantly decreases. This reduction is primary due to the adsorbent surface becoming less positively charged or even negatively charged at higher pH levels, leading to electrostatic repulsion between the adsorbent and the negatively charged HA molecules. Furthermore, it was demonstrated that LFTCO-0.3 not only possesses a wide range of adsorption adaptability but also exhibits excellent removal performance for various types of contaminants in water, especially for anionic contaminants (Supplementary Fig. S6).\u003c/p\u003e \u003cp\u003eThe adsorption kinetics depend on the physical and chemical properties of the adsorbent, which influence the adsorption mechanisms. To model the experimental data of HA adsorption onto LFTCO-0.3, pseudo-first order kinetic (PFO), pseudo-second order kinetic (PSO), and intra-particle diffusion (ID) models were employed (Supplementary Text S2)\u003csup\u003e\u003cspan citationid=\"CR73\" class=\"CitationRef\"\u003e73\u003c/span\u003e\u003c/sup\u003e. The fitting curves are shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ee and Supplementary Fig. S7b-c, and the corresponding kinetic parameters are presented in Supplementary Table S2. The ID model fitting yield correlation coefficients (R\u003csup\u003e\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e\u003c/sup\u003e) ranging from 0.341\u0026thinsp;~\u0026thinsp;0.945, indicating that intra-particle diffusion was not the rate-determining step in the adsorption process\u003csup\u003e\u003cspan citationid=\"CR74\" class=\"CitationRef\"\u003e74\u003c/span\u003e\u003c/sup\u003e. In comparison, the PFO model showed lower correlation with the experimental data (R\u003csup\u003e2\u003c/sup\u003e\u0026thinsp;=\u0026thinsp;0.834\u0026thinsp;~\u0026thinsp;0.990) than the PSO model, which exhibited an excellent fit with high correlation coefficients (R\u003csup\u003e2\u003c/sup\u003e\u0026thinsp;\u0026gt;\u0026thinsp;0.996). Additionally, the equilibrium adsorption capacities calculated using the PSO kinetic equation (Supplementary Equation S4) were consistent with the experimental data. Therefore, the adsorption of HA onto LFTCO-0.3 is better described by the PSO model, suggesting that the adsorption process is predominantly governed by chemisorption, with physisorption playing a secondary role. To investigate the relationship between adsorption capacity and equilibrium concentration, both Langmuir and Freundlich isotherm models were applied\u003csup\u003e\u003cspan citationid=\"CR75\" class=\"CitationRef\"\u003e75\u003c/span\u003e\u003c/sup\u003e. The correlation coefficients (R\u003csup\u003e\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e\u003c/sup\u003e) and corresponding parameters for both models are listed in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ef and Supplementary Table S3. The Langmuir model, with a correlation coefficient of R\u003csup\u003e2\u003c/sup\u003e\u0026thinsp;=\u0026thinsp;0.983, provided a better fit to the experimental data better than the Freundlich model (R\u003csup\u003e2\u003c/sup\u003e\u0026thinsp;=\u0026thinsp;0.979). This indicates that the adsorption process follows monolayer adsorption, primarily characterized by chemisorption\u003csup\u003e\u003cspan citationid=\"CR76\" class=\"CitationRef\"\u003e76\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eThermodynamic analysis further elucidated the significant role of temperature in the adsorption process from an energy perspective. For practical applications, thermodynamic changes were studied at 298 K, 308 K, and 318 K. As the adsorption temperature increased, the adsorption performance of LFTCO-0.3 for HA improved, and the thermodynamic equilibrium constant (\u003cem\u003eK\u003c/em\u003e\u003csub\u003ed\u003c/sub\u003e) also increased. The results (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003eh and Supplementary Table S4) showed that \u003cem\u003e∆G\u003c/em\u003e\u0026thinsp;\u0026lt;\u0026thinsp;0, indicating that the adsorption process is spontaneous and fall within the range of physical and chemical adsorption (-20 ~ -40 kJ\u0026middot;mol\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e)\u003csup\u003e77\u003c/sup\u003e. Furthermore, the absolute value of \u003cem\u003e∆G\u003c/em\u003e increased with increasing temperature, confirming the spontaneity of the adsorption process at higher temperatures. The positive value of \u003cem\u003e∆S\u003c/em\u003e suggests an increase in the enthalpy at the solid-liquid interface during adsorption, reflecting greater dispersal and interaction of HA molecules on the LFTCO-0.3 interface. This enhanced the solid-liquid interfacial area, promoting further adsorption. Additionally, \u003cem\u003e∆H\u003c/em\u003e\u0026thinsp;\u0026gt;\u0026thinsp;0 indicates that the adsorption process is endothermic, implying that higher temperatures favor adsorption. These results demonstrated that the adsorption of HA onto LFTCO-0.3 is a spontaneous, endothermic chemical process with improved performance at elevated temperatures.\u003c/p\u003e\n\u003ch3\u003eHydrophilicity and structural defects in LFTCO adsorbent\u003c/h3\u003e\n\u003cp\u003eLow-Field Nuclear Magnetic Resonance (LF-NMR) was used to quantify the surface hydrophilicity of water trapped in the absorbents. Compared to pure water, the presence of the adsorbent causes the water to enter nanoconfined regions. The LF-NMR characterization revealed that the T\u003csub\u003e2\u003c/sub\u003e relaxation times of LFO and LFTCO were 932.4 and 142.8 ms, respectively (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ei). Given equal amounts of adsorbent and solvent in both samples, the transverse relaxation time (T\u003csub\u003e2\u003c/sub\u003e) exhibited a negative correlation with the bound water content\u003csup\u003e\u003cspan citationid=\"CR78\" class=\"CitationRef\"\u003e78\u003c/span\u003e\u003c/sup\u003e. From LFO to LFTCO-0.3, protons adsorbed on the particle surfaces become more tightly bound, significantly shortening the NMR relaxation time and increasing the bound water content. This increase is primarily due to the improved hydrophilicity of the LFTCO-0.3 surface achieved through doping modification. The presence of more bound water on and within the adsorbent indirectly enhances its adsorption properties. This finding aligns with the type and content of surface oxygen in perovskite oxides determined by XPS O 1s spectroscopy (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ef). The ratio of oxygen vacancies to lattice oxygen (O\u003csub\u003eV\u003c/sub\u003e/O\u003csub\u003eL\u003c/sub\u003e), which indicates the abundance of oxygen vacancies in the material, increased from 0.61 in LFO to 1.05 in LFTCO-0.3 (Supplementary Table S5). The dual doping of Ti and Co in LFTCO-0.3 promotes the formation of structural defects, generating more oxygen vacancies and active sites, thereby improving adsorption performance. Compared with LFO, LFTCO-0.3 possesses a larger number of oxygen vacancies and active sites, significantly enhancing its adsorption capacity.\u003c/p\u003e \u003cp\u003eThe Independent Gradient Model based on Hirshfeld partition (IGMH) is a computational interaction method that utilizes the electron density gradient and has gained widespread popularity due to its universality and robustness. We applied IGMH to calculate the adsorption behavior of HA molecules on the surface of LaFeO\u003csub\u003e3\u003c/sub\u003e crystals. The results indicate that pristine LaFeO\u003csub\u003e3\u003c/sub\u003e crystals possess notable adsorption capacity for HA molecules (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ej), mainly driven by interactions between Fe and O atoms, with HA molecules being adsorbed onto the crystal surface through two or more Fe-O interactions. As discussed previously, Co doping leads to a transition of the crystal material from an antiferromagnetic to a ferromagnetic state. Given that closed-shell organic molecules like HA are diamagnetic, the enhanced adsorption performance of HA on the Co-doped LaFeO\u003csub\u003e3\u003c/sub\u003e surface is relatively modest (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ek). In contrast, Ti doping reverts the material back to an antiferromagnetic state, restoring these interactions. Due to the B-site dual-doping of Co and Ti during synthesis, the number of adsorption sites and anisotropy of the crystal increase, leading to a stronger adsorption capacity compared to the pristine LaFeO\u003csub\u003e3\u003c/sub\u003e crystals (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003el). The dual-doping effectively enhances the crystal\u0026rsquo;s ability to adsorb HA molecules, showcasing a notable improvement in adsorption performance.\u003c/p\u003e \u003cdiv id=\"Sec8\" class=\"Section2\"\u003e \u003ch2\u003eDynamic HA adsorption and model analysis on LFTCO\u003c/h2\u003e \u003cp\u003eTo simulate real-world applications of adsorbents, we systematically investigated the influence of influent flow rate, bed height, feed concentration, and feed pH on the dynamic adsorption performance of LFTCO-0.3 (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ea and Supplementary Text S3). The breakthrough curves under various conditions exhibited an S-shaped profile, indicating similar trends across different parameters. Over time, all adsorption curves followed a pattern characterized by an initial gentle slope, transitioning to a steep incline, and subsequently leveling off (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ec-f).\u003c/p\u003e \u003cp\u003eThe flow rate significantly influences the contact time between the adsorbent and the pollutant during dynamic adsorption, thereby affecting the overall adsorption efficiency. We examined the effect of different influent flow rates ranging from 0.7 to 4.0 mL/min at fixed HA concentration and bed height (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ec). At lower flow rates, the contact time between HA molecules and LFTCO-0.3 increased, allowing for more prolonged and effective interactions. Conversely, higher flow rates shortened the contact time, limiting external mass transfer to the adsorbent surface\u003csup\u003e\u003cspan citationid=\"CR79\" class=\"CitationRef\"\u003e79\u003c/span\u003e\u003c/sup\u003e. This resulted in the rapid passage of HA solution through the fixed bed column, decreasing interaction time and consequently lowering adsorption efficiency, which led to higher effluent concentrations. Furthermore, higher flow rates caused a greater volume of HA solution to pass through the adsorbent per unit time, thereby shortening the breakthrough time. As the flow rate increased, both the breakthrough and adsorption saturation points shifted to the left, resulting in shorter breakthrough and saturation times. In addition, with increasing flow rate, the adsorption capacity at saturation gradually decreased. Based on these observations, a flow rate of 1.4 mL/min was selected as the optimal condition for subsequent experiments.\u003c/p\u003e \u003cp\u003eThe bed height, which determines the amount of adsorbent in the column, plays a crucial role in the dynamic adsorption process. An increase in bed height results in more active adsorption sites, enhancing the treatment capacity for polluted wastewater and reducing the frequency of desorption. To further examine this, we studied the influence of various bed heights on dynamic adsorption performance (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ed). The results indicated that as the bed height increased, the breakthrough and adsorption saturation time also increased significantly. A larger bed height, associated with a greater amount of adsorbent, led to an increased total number of active sites within the fixed bed column. This enhancement facilitated longer and more substantial contact between HA and the adsorbent, contributing to improved adsorption capacity. An increase in bed height corresponded to a longer breakthrough time, a gentler slope of the breakthrough curve, and an enlarged mass transfer zone. These factors collectively enhanced the overall adsorption capacity. When selecting the optimal bed height, it is essential to consider the amount of adsorbent used, adsorption efficiency, operational time, and economic viability. Based on these considerations, a bed height of 2.4 cm was determined to be optimal for this experiment.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eFeed concentration is a key factor affecting the dynamic adsorption performance, as the concentration gradient between the pollutant and the adsorbent surface provides the driving force for mass transfer and promotes adsorption. As the feed concentration of HA increases, the corresponding breakthrough and adsorption saturation times decrease (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ee). As the feed concentration rises, the slope of the breakthrough curve steepens, and the time to reach the breakthrough point shortens. This occurs because a larger concentration difference between the surface of LFTCO-0.3 and HA in solution creates a greater driving force for mass transfer, allowing HA molecules to more rapidly occupy the adsorption sites on the surface of LFTCO-0.3\u003csup\u003e80\u003c/sup\u003e. This accelerates the rate of adsorption, causing the breakthrough and saturation points to be reached more quickly. Considering the influence of feed concentration on adsorption saturation time, a concentration of 30 mg/L was selected for subsequent experiments.\u003c/p\u003e \u003cp\u003eThe pH of the feed solution also significantly affects the dynamic adsorption performance by influencing the charge interactions between the adsorbent and the adsorbate. Dynamic adsorption experiments were carried out at different pH levels to understand their impact on HA adsorption (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ef). Under acidic conditions, LFTCO-0.3 exhibits an enhanced adsorption capacity for HA. Conversely, under alkaline conditions, the breakthrough time is significantly shortened, and the adsorption capacity for HA is reduced. This phenomenon aligns with previous analyses of electrostatic interactions, solubility, and morphological changes at different pH levels. The results indicate that LFTCO-0.3 is effective for HA treatment under acidic conditions.\u003c/p\u003e \u003cp\u003eGiven the complexity of the dynamic adsorption process, which involves multiple components (solvent, adsorbate, adsorbent) and numerous operating conditions, we utilized several widely recognized dynamic adsorption models to fit the breakthrough curve of HA adsorption onto LFTCO-0.3, aiming to better understand its behavior and underlying mechanisms (Supplementary Text S3).\u003c/p\u003e \u003cp\u003eThe Bohart-Adams Surface Diffusion-Time (BDST) model was employed to predict the breakthrough times for different bed heights using the breakthrough curve data. For our analysis, we performed data fitting for varying bed heights at fixed influent flow rate and feed concentration. The linear fitting results (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003eb) demonstrated a high degree of accuracy, with a regression coefficient R\u003csup\u003e\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e\u003c/sup\u003e of 0.998. Moreover, the errors between the predicted breakthrough times from the BDST model and the actual breakthrough times were less than 2% (Supplementary Table S6). To further validate the BDST model, we calculated theoretical breakthrough times at various feed concentrations and flow rates using the fitted equation and compared them with the actual data. The errors between the theoretical and actual breakthrough times remained consistently low, less than 4% and 7% (Supplementary Tables S7 and S8), respectively. These findings indicate that the BDST model is highly applicable for modeling the dynamic adsorption process of HA onto LFTCO-0.3 and can reliably predict breakthrough times under different solution flow rates and concentrations.\u003c/p\u003e \u003cp\u003eThe Thomas model was also applied to estimate the equilibrium adsorption capacity and adsorption rate constant for studying the adsorption kinetics. The Thomas model fitting parameters (Supplementary Table S9) revealed R\u003csup\u003e\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e\u003c/sup\u003e values greater than 0.971. The adsorption rate constant \u003cem\u003eK\u003c/em\u003e\u003csub\u003e\u003cem\u003eTh\u003c/em\u003e\u003c/sub\u003e decreased with increasing bed height, increased with rising flow rate and feed concentration, and varied nonlinearly with pH (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003eg-j). The concordance between experimental and theoretical adsorption capacities indicates that the Thomas model accurately describes the dynamic adsorption of HA onto LFTCO-0.3, suggesting that internal and external diffusion are not the primary rate-determining factors\u003csup\u003e\u003cspan citationid=\"CR81\" class=\"CitationRef\"\u003e81\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eThe Yoon-Nelson model was utilized to evaluate the time \u003cem\u003eτ\u003c/em\u003e required for the effluent concentration of HA to reach half the feed concentration and the adsorption rate constant \u003cem\u003eK\u003c/em\u003e\u003csub\u003e\u003cem\u003eYN\u003c/em\u003e\u003c/sub\u003e. According to Supplementary Equation S15, time and ln (C\u003csub\u003et\u003c/sub\u003e/(C\u003csub\u003e0\u003c/sub\u003e-C\u003csub\u003et\u003c/sub\u003e)) were fitted linearly, and the fitting curves are shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ek-n. The theoretical τ values indicated that the breakthrough time increased with bed height and decreased with higher influent flow rate and concentration, as well as increased pH, before stabilizing. The R\u003csup\u003e\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e\u003c/sup\u003e values for the fits were greater than 0.971, closely aligned with the Thomas model results (Supplementary Table S9). These findings confirm that the Yoon-Nelson model accurately predicts the breakthrough time and rate constant K\u003csub\u003eYN\u003c/sub\u003e for the adsorption process using LFTCO-0.3, making it a reliable method for modeling dynamic adsorption behaviors.\u003c/p\u003e \u003c/div\u003e\n\u003ch3\u003eCyclic performance and regeneration of LFTCO adsorbent\u003c/h3\u003e\n\u003cp\u003eWe evaluated the reusability of LFTCO-0.3 for the adsorption of HA to assess its potential for industrial applications. Figure\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ea illustrates a schematic diagram of the adsorption-desorption cycle. Under static condition at pH 7.0, 0.2 g/L of absorbent was added to 200 ml of HA solution (\u003cem\u003eC\u003c/em\u003e\u003csub\u003e\u003cem\u003eHA\u003c/em\u003e\u003c/sub\u003e = 30 mg/L). After the adsorption process was complete, LFTCO-0.3 was recovered using a strong magnet. The adsorbent was then immersed in a diluted hydrogen peroxide (H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e) solution to facilitate chemical desorption, leveraging the Fenton properties inherent in ferrite to generate hydroxyl radicals that break down the adsorbed HA. Following three washes with deionized water and drying at 60℃, the adsorbent was reused in the next adsorption experiment. After five adsorption-desorption cycles, the removal efficiency of LFTCO-0.3 to HA remained at 89.87% (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003eb), demonstrating that the magnetic adsorbent retained its adsorption performance after chemical desorption. This also suggests that LFTCO-0.3 maintained its Fenton activity and magnetism throughout the cycles. To understand the molecular interactions, density functional theory (DFT) calculations were performed to determine the molecular orbital structure (Supplementary Fig. S8), which confirmed the feasibility of using H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e for the oxidative removal of HA molecules. The calculations indicated favorable interactions between H₂O₂, LFTCO-0.3, and the adsorbed HA, facilitating the oxidative degradation of HA during the desorption process.\u003c/p\u003e \u003cp\u003eMoreover, the concentrations of dissolved metal ion gradually decreased with each cycle. After the fifth cycle, the concentrations of La\u003csup\u003e3+\u003c/sup\u003e, Co\u003csup\u003e3+\u003c/sup\u003e, Fe\u003csup\u003e3+\u003c/sup\u003e, and Ti\u003csup\u003e4+\u003c/sup\u003e were 0.017 mg/L, 0.048 mg/L, 0.026 mg/L, and 0.012 mg/L, respectively (Supplementary Fig. S9). These levels are below the national wastewater discharge standards, indicating minimal leaching of metal ions during regeneration. Furthermore, the crystal structure of the perovskite adsorbent remained unchanged after five cycles, as confirmed by X-ray diffraction analysis, indicating good structural stability (Supplementary Fig. S10).\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eTo investigate the regeneration and stability performance of LFTCO-0.3 during the dynamic adsorption process, we conducted five cycles of adsorption-desorption experiments using a fixed bed column packed with LFTCO-0.3, as illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ec. The breakthrough curves (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ed) indicate that LFTCO-0.3 maintained high adsorption performance after five cycles. As the cyclic experiment progressed, both the time to reach the breakthrough point and the saturation time decreased, suggesting a reduced adsorption capacity of LFTCO-0.3 for HA. This reduction is likely due to incomplete desorption within a fixed recovery period of 20 min. Despite this, LFTCO-0.3 exhibits good stability and regenerative capability, as confirmed by X-ray diffraction analysis.\u003c/p\u003e \u003cp\u003eNotably, LFTCO-0.3 ranks among the highest in adsorption capacities for HA when compared to other adsorbents reported in the literature (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ee; Supplementary Table S10). It rapidly achieves HA removal with a maximum adsorption capacity of 381 mg/g under 2 hr (Supplementary Table S2; Detailed comparison and methodology are provided in the Supporting Information). In addition, traditional regeneration methods for reported adsorbents typically involve high-temperature calcination or solvent elution using agents like NaOH, resulting in elevated energy consumption and potential secondary pollution\u003csup\u003e\u003cspan additionalcitationids=\"CR83\" citationid=\"CR82\" class=\"CitationRef\"\u003e82\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR84\" class=\"CitationRef\"\u003e84\u003c/span\u003e\u003c/sup\u003e. In contrast, our adsorbent can be regenerated in under 20 min (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ed) through the Fenton reaction, facilitated by LFTCO\u0026rsquo;s ability to generate radicals. The impressive adsorption and regeneration properties of LFTCO-0.3 make it particularly suitable for use in adsorption columns. Its easy dispersion and straightforward magnetic separation also allow its application in existing AOP tanks without requiring structural modifications to sewage treatment facilities. The versatility of LFTCO-0.3 supports flexible application scenarios. These findings suggest that LFTCO-0.3 could serve as an environmentally friendly and magnetic adsorbent with excellent HA removal performance, offering significant advantages in ease of regeneration, stability, and reduced environmental impact compared to conventional adsorbents.\u003c/p\u003e"},{"header":"Conclusions","content":"\u003cp\u003eWe developed LFTCO, a dual-doped perovskite oxide adsorbent synthesized via the sol-gel method, featuring Co and Ti doping at the B-site. LFTCO exhibits superior adsorption performance for NOM, particularly HA. Kinetic and thermodynamic analyses confirm that the adsorption mechanism is predominantly chemical, augmented by spontaneous endothermic physical interactions. Dynamic adsorption experiments demonstrate LFTCO\u0026rsquo;s effectiveness for continuous HA removal, with predictive modeling using BDST, Thomas, and Yoon-Nelson models providing reliable estimates for adsorption capacity and breakthrough times. LFTCO\u0026rsquo;s excellent Fenton catalytic activity and magnetic properties enable efficient regeneration and reuse through magnetic separation, fixed-bed adsorption, and the Fenton reaction. This process circumvents the high energy consumption and potential secondary pollution associated with traditional regeneration methods. The versatility of LFTCO allows seamless integrated into adsorption columns and AOP tanks without requiring structural modifications to existing sewage treatment plants. Its easy dispersion and straightforward magnetic separation further broaden its application potential in diverse wastewater treatment scenarios. Overall, LFTCO emerges as a highly promising adsorbent for water treatment, offering significant advantages in adsorption efficiency, ease of regeneration, stability, and reduced environmental impacts. Its adoption across diverse wastewater treatment settings could substantially enhance the removal of NOM, enhance water quality management, and promote more sustainable treatment processes.\u003c/p\u003e"},{"header":"Materials and methods","content":"\u003cdiv id=\"Sec12\" class=\"Section2\"\u003e \u003ch2\u003eChemical reagents\u003c/h2\u003e \u003cp\u003eHA was purchased from Alfa Aesar (China) Chemical Co., Ltd. Methylene blue, Congo red, Rhodamin B, sodium hydroxide, and anhydrous ethanol were purchased from Sinopharm Chemical Reagent Co., Ltd. Oxytetracycline hydrochloride, sodium citrate, ammonia, hydrochloric acid, and hydrogen peroxide were purchased from Aladdin Reagent (Shanghai) Co., Ltd. Tetrabutyl titanate and polyethylene glycol 600 were purchased from Shanghai Lingfeng Reagent Co., Ltd. La(NO\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e3\u003c/sub\u003e\u0026middot;6H\u003csub\u003e2\u003c/sub\u003eO, Fe(NO\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e3\u003c/sub\u003e\u0026middot;9H\u003csub\u003e2\u003c/sub\u003eO, and Co(NO\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e3\u003c/sub\u003e\u0026middot;6H\u003csub\u003e2\u003c/sub\u003eO were purchased from Shanghai Macklin Biochemical Co., Ltd. The chemicals used in this investigation were of analytical grade and no additional purification steps were conducted on any of the reagents. All solutions were prepared using deionized water (DI).\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec13\" class=\"Section2\"\u003e \u003ch2\u003eSynthesis of LFTCO adsorbents\u003c/h2\u003e \u003cp\u003eLaFeO\u003csub\u003e3\u003c/sub\u003e (LFO) and LaFe\u003csub\u003e0.55\u003c/sub\u003eCo\u003csub\u003e0.45\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e (LFCO) perovskite oxides were synthesized using a sol-gel method followed by calcination. First, the metal compounds of La(NO\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e3\u003c/sub\u003e\u0026middot;6H\u003csub\u003e2\u003c/sub\u003eO, Fe(NO\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e3\u003c/sub\u003e\u0026middot;9H\u003csub\u003e2\u003c/sub\u003eO, and Co(NO\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e\u0026middot;6H\u003csub\u003e2\u003c/sub\u003eO were mixed, stirred, and dissolved in a beaker. The molar ratio was La: Fe\u0026thinsp;=\u0026thinsp;1:1 for preparing LFO and La: Fe: Co\u0026thinsp;=\u0026thinsp;1:0.55:0.45 for preparing LFCO. Sodium citrate was added to the mixed metal solution to achieve a molar ratio of 1:5 between metal cations and citrate anions. The pH of the metal solution was adjusted to 4 using 20% ammonia solution. The mixed metal solution was stirred continuously at 80\u0026deg;C until it transformed into a sol-gel state. The resulting wet gel was placed in a preheated oven and dried at 120\u0026deg;C overnight. The dried gel was then placed in a muffle furnace and heated from 20\u0026deg;C to 300\u0026deg;C at a rate of 5\u0026deg;C/min. It was then held at 300\u0026deg;C for 3 h before being heated further to the final temperature of 700\u0026deg;C, where it was held for 5 h. After natural cooling of the muffle furnace, the desired product (LFO and LFCO) was obtained.\u003c/p\u003e \u003cp\u003eLaFe\u003csub\u003e0.55\u003c/sub\u003eTi\u003csub\u003e0.45\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e (LFTO) and LaFe\u003csub\u003e0.55\u003c/sub\u003eCo\u003csub\u003e0.45\u0026minus;x\u003c/sub\u003eTi\u003csub\u003ex\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e (LFTCO) were synthesized by adding titanium dioxide sol to the above mixed metal solution. Titanium dioxide sol was prepared by adding tetrabutyl titanate, anhydrous ethanol, PEG600, and deionized water in a molar ratio of 3:12:3:1 to form a transparent sol. The prepared Ti dioxide sol was slowly added into the mixed metal solution and stirred sufficiently for 1 hour at 50\u0026deg;C. The molar ratio was La:Fe:Ti\u0026thinsp;=\u0026thinsp;1:0.55:0.45 for preparing LFTO. For the preparation of dual-doped LaFe\u003csub\u003e0.55\u003c/sub\u003eCo\u003csub\u003e0.45\u0026minus;x\u003c/sub\u003eTi\u003csub\u003ex\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e (LFTCO, x\u0026thinsp;=\u0026thinsp;0.1, 0.2, 0.3, and 0.4), the molar ratio is La:Fe:Co:Ti\u0026thinsp;=\u0026thinsp;1:0.55:0.45-x:x. For example, the preparation of dual-doped LFTCO-0.3, the corresponding molar ratio is La:Fe:Co:Ti\u0026thinsp;=\u0026thinsp;1:0.55:0.15:0.3. Sodium citrate and ammonia solution were then added sequentially to the mixed metal solution in the same steps as above. The mixed metal solution was stirred continuously at 80\u0026deg;C until it transformed into a sol-gel state. The perovskite oxide-type adsorbent, LFTO and LFTCO were subsequently obtained using the same dry and annealing conditions.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec14\" class=\"Section2\"\u003e \u003ch2\u003eMaterial characterizations\u003c/h2\u003e \u003cp\u003eThe surface morphology of metal oxide was characterized by scanning electron microscopy (SEM, HITACHI S-4800, Japan). The elemental composition of metal oxide was obtained by energy-dispersive X-ray spectroscopy (EDX, Horiba, Japan). The morphological structure was further analyzed by transmission electron microscopy (TEM, FEI Tecnai F20, USA). The crystal morphology of the perovskite oxide-type adsorbents was analyzed by X-ray diffraction spectroscopy (XRD, RIGAKU MiniFlex600, Japan). The functional groups of perovskite oxide-type adsorbents were identified by Fourier transform infrared spectroscopy (FT-IR, Thermo Nicolet8700, USA). The textural properties of the perovskite oxide-type adsorbents were assessed by N\u003csub\u003e2\u003c/sub\u003e adsorption/desorption analysis (BET, Micromeritics ASAP 2460, USA). Metal cation states and oxygen forms were investigated by X-ray photoelectron spectrometry (XPS, ESCALAB 250XI, USA). Ferromagnetism was measured using a vibrating sample magnetometer (VSM, Quantum Design Dyna Cool, USA) at room temperature. The zeta potential of perovskite oxide-type adsorbents in aqueous solution was determined by laser scattering method (Malvern Nano ZS90, UK). Additionally, the absorbance of HA at 254 nm was determined by UV-visible spectrophotometry (Perkin Elmer Lambda950, USA). The dissolution concentrations of leached metal ions were measured by inductively coupled plasma spectrometry (ICP, Optima 7000DV, USA). The hydrophilicity and water distribution characteristics of the adsorbents were characterized by low-field nuclear magnetic resonance spectroscopy (LF-NMR, NM42-40H-I, Suzhou Niumag).\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec15\" class=\"Section2\"\u003e \u003ch2\u003eComputational simulation\u003c/h2\u003e \u003cp\u003eDensity Functional Theory (DFT) calculations were performed on the small molecules, lanthanum ferrate crystals, and their doped variants involved in the experiments. The details are described in the Supplementary Text.\u003c/p\u003e \u003c/div\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eAcknowledgements\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThis work was financially supported by the National Natural Science Foundation of China (21921006, 22208147, 22250410273, 22478177), Jiangsu Provincial Department of Science and Technology (BK20232010), and Jiangsu Provincial Key Research and Development Project (BE2023058).\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAuthor contributions\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eLekai Zhao: Writing – Original draft, Methodology, Investigation, Formal analysis, Data curation, Conceptualization. Shuang Han: Writing – Review \u0026amp; editing, Methodology, Investigation, Formal analysis, Data curation, Conceptualization. Xiao Ma: Methodology, Formal analysis. Ming Zhou: Methodology, Conceptualization. Qiuyue Wang: Methodology, Formal analysis. Shasha Feng: Methodology, Formal analysis. Zhaoxiang Zhong: Writing – Review \u0026amp; editing, Supervision, Funding acquisition. Ze-Xian Low: Writing – Review \u0026amp; editing, Visualization, Supervision, Project administration, Funding acquisition. Weihong Xing: Conceptualization, Supervision, Project administration, Funding acquisition.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eCompeting Interest\u003c/strong\u003e\u003cstrong\u003es\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe authors declare no competing interests.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eSupplementary information\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe online version contains supplementary material available at\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n\u003cli\u003eFahrenkamp-Uppenbrink, J. 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Fabrication of cotton linter-based adsorbents by radiation grafting polymerization for humic acid removal from aqueous solution. \u003cem\u003ePolymers\u003c/em\u003e. \u003cstrong\u003e11,\u003c/strong\u003e 962 (2019).\u003c/li\u003e\n\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":true,"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":"nature-portfolio","isNatureJournal":true,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"","title":"Nature Portfolio","twitterHandle":"","acdcEnabled":false,"dfaEnabled":false,"editorialSystem":"ejp","reportingPortfolio":"","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"perovskite oxide, B-site doping, humic acid, dynamic adsorption, Fenton","lastPublishedDoi":"10.21203/rs.3.rs-5225322/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-5225322/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eHumic acid (HA), a complex organic compound of natural matter, is harmless on its own but can form carcinogenic disinfection byproducts such as trihalomethanes and haloacetic acids during water chlorination and disinfection processes, posing serious risks to aquatic organisms and human health. We present a B-site dual-metal-doping strategy to fabricate ferromagnetic perovskite-type adsorbents for rapid and efficient HA degradation. Through B-site modification with Ti and Co, the resulting perovskite absorbent exhibits a rapid HA adsorption rate with a high adsorption capacity of 381 mg/g. We demonstrate that the adsorbent can be regenerated \u003cem\u003ein situ\u003c/em\u003e or magnetically recovered for Fenton regeneration. The dynamic adsorption behavior of HA is accurately described and predicted by the Bed Depth Service Time (BDST), Thomas, and Yoon-Nelson models while computational simulations provide insights into the interactions between the perovskite adsorbent and HA molecules. Our findings reveal the potential of perovskite materials as highly effective catalytic adsorbents for organic compounds that can be efficiently regenerated, paving the way for their development in water remediation applications.\u003c/p\u003e","manuscriptTitle":"Dual-Metal-Doped Perovskite Adsorbents for Efficient Removal of Humic Acid","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2024-12-11 13:58:54","doi":"10.21203/rs.3.rs-5225322/v1","editorialEvents":[],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"nature-communications","isNatureJournal":true,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"NCOMMS","sideBox":"Learn more about [Nature Communications](http://www.nature.com/ncomms/)","snPcode":"","submissionUrl":"https://mts-ncomms.nature.com/","title":"Nature Communications","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"ejp","reportingPortfolio":"Nature Communications","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"d902454f-8022-473d-92c0-0fa7b07b6baf","owner":[],"postedDate":"December 11th, 2024","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[{"id":39856115,"name":"Physical sciences/Engineering/Chemical engineering"},{"id":39856116,"name":"Physical sciences/Chemistry/Chemical engineering"}],"tags":[],"updatedAt":"2026-04-28T07:10:47+00:00","versionOfRecord":{"articleIdentity":"rs-5225322","link":"https://doi.org/10.1038/s41467-026-70286-6","journal":{"identity":"nature-communications","isVorOnly":false,"title":"Nature Communications"},"publishedOn":"2026-03-12 04:00:00","publishedOnDateReadable":"March 12th, 2026"},"versionCreatedAt":"2024-12-11 13:58:54","video":"","vorDoi":"10.1038/s41467-026-70286-6","vorDoiUrl":"https://doi.org/10.1038/s41467-026-70286-6","workflowStages":[]},"version":"v1","identity":"rs-5225322","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-5225322","identity":"rs-5225322","version":["v1"]},"buildId":"qtupq5eGEP_6zYnWcrvyt","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}