Green Synthesis of CoAl2O4@ZnO nanocomposite using Aamygdalus scoparia Spach gum and its photocatalytic activity for tetracycline degradation

Green Synthesis of CoAl2O4@ZnO nanocomposite using Aamygdalus scoparia Spach gum and its photocatalytic activity for tetracycline degradation | 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 Green Synthesis of CoAl2O4@ZnO nanocomposite using Aamygdalus scoparia Spach gum and its photocatalytic activity for tetracycline degradation Farzaneh Nejadkhorasani, Hassan Zali Boeini, Saeid Taghavi Fardood This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-6515698/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 03 Jan, 2026 Read the published version in Scientific Reports → Version 1 posted 10 You are reading this latest preprint version Abstract A novel CoAl 2 O 4 @ZnO nanocomposite (NC) was synthesized via a green, low-cost, and simple sol-gel method using Amygdalus scoparia Spach gum. The photocatalytic efficacy of the produced CoAl 2 O 4 @ZnO NC was examined for the degradation of tetracycline (TC) under visible light. The CoAl 2 O 4 @ZnO NC analyzed using XRD, BET, UV-Vis-DRS, FESEM, TEM, EDX and Mapping. The XRD analysis confirmed the formation of CoAl 2 O 4 with a cubic spinel structure and ZnO with a hexagonal wurtzite structure. BET analysis revealed a specific surface area of approximately 40.045 m 2 /g. The band gap energy was estimated to be around 3.0 eV using the Tauc equation. The CoAl 2 O 4 @ZnO NC demonstrated significant photocatalytic efficacy, obtaining 93% degradation of tetracycline in 45 min under visible light irradiation. LC-MS analysis identified multiple intermediate products during the comprehensive investigation of the photodegradation mechanism which confirmed the degradation pathway. The addition of ethanol as a scavenger led to reduced photocatalytic activity which demonstrates that hydroxyl radicals (•OH) play a crucial role in the degradation process. The nanocomposite maintained stability and photocatalytic efficiency throughout five repeated tests which showed minimal reduction in activity. Physical sciences/Chemistry/Biosynthesis Physical sciences/Chemistry/Catalysis/Photocatalysis Green synthesis Tetracycline Degradation photocatalytic activity Nanocomposite Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 Figure 9 Figure 10 Figure 11 1. Introduction The increasing variety of water pollutants demands enhanced international attention to health and environmental safeguarding 1 – 3 . A significant category comprises bioactive chemical residues from medical and hygiene consumer items. These pollutants are acknowledged as environmental hazards due to their potential physiological impacts on humans and other organisms, even at minimal concentrations 4 , 5 . These chemical contaminants have become pervasive in the natural world as they are unable to be efficiently eliminated by traditional wastewater treatment processes due to their harmful effects and resistance to degradation 6 – 8 . The elimination of these pollutants is of significant concern in health and safety management due to their potential detrimental impacts on humans and ecosystems. Modern oxidation technologies, particularly semiconductor-based photocatalysis, have acquired prominence for their removal due to their rapid degradation rates, cost-effectiveness, and mineralisation capabilities 9 – 12 . Future research on nanoparticles and nanomaterials needs environmentally friendly synthesis methods 13 . An eco-friendly strategy is defined as one that operates within the framework of green chemistry and green engineering to prevent the use and generation of harmful and undesirable substances, hence safeguarding the environment and living beings 14 – 16 . Semiconductors with a wide bandgap, such as SnO 2 17 , ZnO 18 , 19 and TiO 2 20 , have been extensively investigated due to their excellent chemical stability and strong oxidizing ability under UV irradiation. Nonetheless, their significant bandgaps (Eg > 3.0 eV) limit absorption to the ultraviolet spectrum, a minor part of solar radiation. This limitation significantly reduces their photocatalytic efficiency under visible light. Consequently, recent research has focused on modifying or combining them with narrow bandgap materials to enhance visible light absorption and improve photocatalytic performance. Many studies have concentrated on narrow band gap semiconductors, and spinels AB 2 O 4 are particularly fascinating owing to their chromatic characteristics and moderate conductivity 21 , 22 . A is usually divalent, while B is a 3D metal 23 , 24 . Spinels serve as catalyst supports due to their stability and strong resistance to acids and alkalis 25 . These materials are utilized for their unique optical and magnetic characteristics in various applications 26 , 27 . CoAl 2 O 4 features a spinel structure with distinct occupancy of aluminum and cobalt ions 28 . This has motivated advancements in photodegradation via the integration of semiconductors with diverse bandgaps. Current investigations emphasize the creation of environmentally friendly, facilely synthesized, and lightweight materials 29 , 30 . The progression of photocatalytic materials exhibiting enhanced performance under natural conditions is critical. CoAl 2 O 4 and ZnO are noted for their high surface area and physicochemical stability, contributing to their improved photocatalytic efficiency due to successful electron-hole pair separation 31 – 33 . A sustainable sol–gel technique was utilized for the synthesis of CoAl 2 O 4 @ZnO nanocomposite. This eco-friendly synthesis method presents numerous benefits compared to traditional chemical approaches, such as ease of use, cost efficiency, safety, environmental suitability, and the removal of organic surfactants. The characteristics of the CoAl 2 O 4 @ZnO NC were analyzed. This study is the first to document the photocatalytic degradation of tetracycline hydrochloride via CoAl 2 O 4 @ZnO. The degradation of TC was assessed under varied conditions to identify optimal parameters such as nanocomposite dosage, initial TC concentration, light/dark settings, irradiation duration, and reusability. Figure 1 shows the chemical structures of Tetracycline (TC). 2. Experimental 2.1. Materials and characterization The Amygdalus scoparia Spach gum was collected from the Zagros Mountains in Ilam, Iran. Aluminium nitrate nonahydrate (Al(NO 3 ) 3 ·9H 2 O), cobalt(II) nitrate hexahydrate (Co(NO 3 ) 2 ·6H 2 O), and zinc nitrate hexahydrate (Zn(NO 3 ) 2 ·6H 2 O) were obtained from Merck Company. The XRD pattern of CoAl 2 O 4 @ZnO NC was obtained by employing an X'Pert-PRO advanced diffractometer. The radiation source used was Cu-K, which has a wavelength of 1.5406 Å. The CoAl 2 O 4 @ZnO NC was characterized using an EM 208S microscope for TEM and a Tescan Mira3 microscope for SEM, along with energy-dispersive X-ray (EDX) analysis and mapping. BET data analysis was conducted via a Belsorp Mini II, and UV-Vis absorption spectra were recorded using a UV-Vis spectrophotometer from the Cary series. The optical properties were analyzed via UV-Vis-DRS spectroscopy, utilizing the Jasco-V670. The band gap (Eg) was determined using Tauc's theory 34 . 2.2. Green synthesis of CoAl 2 O 4 @ZnO Firstly, 0.4 g of the Amygdalus scoparia Spach gum was dissolved in 50 mL of distilled water and agitated at 80°C for 30 minutes to produce a homogenous and translucent gel solution. Subsequently, 2 mmol of Al(NO 3 ) 3 ⋅9H₂O and 1 mmol of Co(NO 3 ) 2 ·6H 2 O were added, and the mixture was stirred in a sand bath at 90°C for 12 h. The resulting precursor was then calcined at 600°C for 4 h to obtain CoAl 2 O 4 nanoparticles. For the synthesis of the CoAl 2 O 4 @ZnO nanocomposite, the gel solution was freshly prepared using the same procedure. Then, 0.1 g of the synthesised CoAl 2 O 4 was dispersed into the gel and treated with ultrasonic irradiation for 4 minutes. Afterwards, 0.5 g of Zn(NO 3 ) 2 ·6H 2 O was added and the suspension was further sonicated for another 4 minutes. The mixture was subsequently stirred in a sand bath at 90°C for 12 hours. Finally, the obtained product was calcined at 500°C for 4 hours to form the CoAl 2 O 4 @ZnO NC. 2.3. Photocatalytic experiment Photodegradation experiments were performed under visible light irradiation inside a box with an 80 W fluorescent lamp (λ > 400 nm). The photocatalytic efficacy of the CoAl 2 O 4 @ZnO nanocomposite was assessed through the degradation of tetracycline (TC) in aqueous solution under ambient conditions. A 50 mL TC solution was employed to ascertain optimal degradation efficiency, while evaluating different factors including CoAl 2 O 4 @ZnO dosage, initial TC concentration, reaction time, light versus dark conditions, and catalyst reusability. The degradation efficiency of TC was analyzed via UV–Vis spectroscopy at λ_max = 371 nm. The following formula was employed to determine the degradation rate of TC. $$\:\text{D}\text{e}\text{g}\text{r}\text{a}\text{d}\text{a}\text{t}\text{i}\text{o}\text{n}=\frac{\left({A}_{0}-{A}_{t}\right)}{{A}_{0}}\times\:100$$ The initial and ultimate absorption at time t 0 and t min are denoted by the symbols A 0 and A t , respectively. 3. Result and discussion 3.1. Characterization XRD analysis was conducted to elucidate the structural characteristics, phases, and crystallite size of the synthesized nanocomposite. The XRD pattern of CoAl 2 O 4 @ZnO NC is shown in Fig. 2 . The XRD pattern of ZnO contains distinctive peaks at 31.95°, 34.66°, 36.47°, 47.72°, 56.75°, 63.10°, 66.49°, 68.16°, 69.17°, 72.72°, and 77.33°, which are associated with the (100), (002), (101), (102), (110), (103), (200), (112), (201), (004), and (202) planes, respectively and match well with pure ZnO (JCPDS 79–0205). The XRD pattern of CoAl 2 O 4 (JCPDS card no. 44–0160) exhibits peaks at 31.40°, 37.01°, 45.04°, 55.82°, 59.46°, 65.39°, 74.62°, and 77.33°, corresponding to the (220), (311), (400), (422), (511), (440), (620), and (533) planes, respectively, consistent with pure CoAl 2 O 4 (JCPDS 03-0896). The crystallite size of the CoAl 2 O 4 @ZnO nanocomposite, estimated using the Scherrer Eq. 3 5 , was found to be approximately 11 nm. The active surface area of the synthesized nanocomposite was assessed using BET. The findings indicate that the nanoparticles possess a specific surface area of 40.045 m²g - ¹, a pore width of 21.048 nm, and a total pore volume of 0.2107 cm³g - ¹. Figure 3 depicts the nitrogen adsorption-desorption isotherm, which, according to the IUPAC classification, shows a typical type IV isotherm with H3 hysteresis loops, indicative of mesoporous materials 36 . The mesoporous CoAl 2 O 4 @ZnO nanocomposites enhance photocatalytic degradation of tetracycline by increasing surface area and light absorption. Figure 4 a shows the SEM image of the CoAl 2 O 4 @ZnO nanocomposite, which exhibits a homogeneous and spherical shape. The TEM image further confirms the synthesis of the CoAl 2 O 4 @ZnO nanocomposite, revealing a uniform particle distribution and spherical morphology, with an average size of approximately 25 − 30 nm (Fig. 4 b). The EDS analysis of the CoAl 2 O 4 @ZnO nanocomposite Fig. 5 reveals the presence of the component elements (Zn, Al, Co, O). Figure 6 shows the EDX mapping of the CoAl 2 O 4 @ZnO nanocomposites, confirming the spatial distribution of Zn, Co, Al, and O within the sample. DRS was performed to examine the optical characteristics of the produced nanocomposite. The band gap of the CoAl 2 O 4 @ZnO NC was determined using the Tauc equation. The Tauc plot of the nanocomposite is illustrated in Fig. 7 . The nanocomposite exhibited a band gap energy of 3 eV. Thus, the reduced band gap indicates that the CoAl 2 O 4 @ZnO NC can be activated with lower photon energy under visible light 37 . 3.2. Photodegradation of TC using CoAl₂O₄@ZnO NC The degradation of TC was carried out using the CoAl 2 O 4 @ZnO photocatalyst under visible light irradiation. The processes evaluated include adsorption (nanocomposite in darkness), photolysis, and photocatalysis. Figure 8 a shows that the degradation efficiencies for adsorption, photolysis, and photocatalysis were 47%, 0%, and 93%, respectively, within 45 minutes. The efficiency of TC photodegradation and photocatalytic activity depends on the optimized usage of the CoAl 2 O 4 @ZnO nanocomposite. Figure 8 b illustrates the effect of catalyst loading (0.02–0.05 g) on tetracycline degradation. Over 45 minutes, the photocatalytic efficiency increased as the catalyst loading rose from 0.02 g to 0.04 g, due to the availability of more active reaction sites. However, when the loading exceeded 0.04 g, the efficiency dropped to 90%, attributed to nanocomposite agglomeration and increased particle collisions. These phenomena led to greater light scattering and reduced light penetration, despite the increase in active sites 38 . The effect of varying initial concentrations of TC on the photodegradation efficiency was investigated in the range of 10–30 mg/L, while other parameters remained constant (0.04 g photocatalyst, 45 min). As shown in Fig. 8 c, TC degradation efficiency decreases as the initial concentration increases. This may be ascribed to decreased photon penetration to the photocatalyst surface and reduced generation of free radicals 39 . The experiment determined the optimal duration for dye degradation by utilizing the optimal catalyst dose and TC concentration across various irradiation times, with findings presented in Fig. 8 d. The λ max of TC occurs at 371 nm, and degradation efficacy is evidenced by a reduction in maximum absorbance as irradiation time increases. It is evident that 93% of TC was degraded within 45 minutes. Scavenger trapping studies were performed to clarify the roles of reactive species in TC photodegradation 40 – 42 . As illustrated in Fig. 9 , the addition of ethanol, a recognized · OH scavenger, significantly reduced the degradation efficiency to 43%, signifying that · OH radicals are the dominant species in the degradation process. The presence of EDTA (h⁺ scavenger) and AgNO₃ (e⁻ scavenger) reduced the degradation efficiency to 78% and 85%, respectively, suggesting that holes and electrons contribute to a lesser extent. Super oxide radicals played a minimal role in the process because the introduction of O₂•⁻ scavenger p-benzoquinone only caused a minor efficiency change. Therefore, the photocatalytic degradation of TC is primarily governed by •OH-mediated mechanisms, with electrons and holes acting as secondary participants. The photodegradation by-products of tetracycline (TC) in the presence of CoAl 2 O 4 @ZnO NC were identified by employing LC-MS analysis under optimized experimental conditions. Figure 10 illustrates the degradation pathways of TC as detected by LC-MS. The photocatalytic activity of CoAl 2 O 4 @ZnO NC facilitates the generation of hydroxyl radicals (•OH) under visible light. The excitation of electrons generates electron-hole pairs that oxidize water, resulting in the formation of •OH radicals that decompose tetracycline. These radicals interact with TC molecules, promoting their degradation. The LC-MS results indicate that the TC molecular structure decomposes, yielding numerous intermediate compounds during photodegradation. Table 1 presents these products along with their degradation intermediates. Studies indicate that the nanocomposite enhances the generation of reactive species, such as •OH radicals, which promote the degradation of the TC molecule via oxidation reactions. The findings offer critical insights into the tetracycline (TC) degradation mechanism and the prospective applications of CoAl 2 O 4 @ZnO NC in wastewater treatment contexts 43 – 46 . Table 1 LC-MS Detection of TC Degradation Products. No Structure m/z No Structure m/z 1 358 2 276 3 260 4 208 5 192 6 118 7 104 8 86 An essential benefit of employing nanocomposite in aqueous purification is their capability to be utilized repeatedly 47 . The stability and photocatalytic efficacy of CoAl 2 O 4 @ZnO NC was examined in five successive experiments under the optimal conditions. The nanocomposite from each experiment was subjected to centrifugation, washed with distilled water, and reutilized to evaluate its reusability. The results, as depicted in Fig. 11 , demonstrated a minimal reduction in degradation efficiency even after five cycles of regeneration. The photocatalytic effectiveness of CoAl 2 O 4 @ZnO NC was assessed against previously documented photocatalysts. Table 2 demonstrates that the synthesized composite exhibited substantial TC degradation efficiency, establishing it as a plausible candidate for wastewater remediation. The enhanced photocatalytic efficacy of the CoAl 2 O 4 @ZnO NC is primarily due to the increased surface area and the synergistic interaction between ZnO and CoAl 2 O 4 , which together enhance light absorption and facilitate efficient charge carrier separation. Table 2 Photocatalytic performance comparison of CoAl 2 O 4 @ZnO with other photocatalysts Photocatalysts Synthesis method Light source TC conc. (ppm) Time/ min Removal efficiency Ref CuAl 2 O 4 /ZnO Hydrothermal Xe lamp,300 W 20 90 100 48 BiOCl 0.5 I 0.5 /NH 2 -MIL-88B(Fe) - Xe lamp, 300 W 120 120 91.15 49 ZnO/CuCo 2 O 4 Hydrothermal LED lamp, 50 W 6.7×10 − 5 mol L − 1 60 100 50 ZnO/CuCo 2 S 4 Hydrothermal Xe lamp, 300W 6.7×10 − 5 mol L − 1 80 100 51 LaFeO 3 /MgFe 2 O 4 Sol-gel Xe lamp, 300 W 300 120 97.01 52 3-In 2 S 3 /Cu 2 S Hydrothermal Xe lamp, 300W 120 150 99.90 53 CuAl 2 O 4 -Cu-Bi 4 O 5 Br 2 (CCB NCs) Ultrasonication-assisted coprecipitation Halogen Lamp, 500 W 75 160 95.4 54 ZnFe 2 O 4 Green hydrothermal - 10 180 94.12 55 FeWO 4 /ZnIn 2 S 4 Solvothermal xenon lamp (500 W 60 60 92.90 56 ZnS/FeWO 4 Hydrothermal - 10 105 91.70 57 Z-scheme ZnWO 4 / Bi 5 O7I Hydrothermal Xe lamp, 300W 20 60 96.80 58 CuO/CoFe₂O₄/MWCNTs Hydrothermal Xe lamp, 150 W 5 120 98.1 59 CoAl 2 O 4 /ZnO Green sol-gel fluorescent lamp, 80W 20 45 93 This work 4. Conclusions In this study, a CoAl 2 O 4 @ZnO nanocomposite was synthesized via a green sol–gel method using Amygdalus scoparia Spach gum as a natural stabilizing agent. Structural, morphological and surface characterizations, including BET, SEM and DRS analysis confirmed the formation of a porous, spherical nanocomposite with a specific surface area of 40.045 m²/g and a band gap of 3.0 eV, enabling efficient activation under visible light. The synergistic interaction between CoAl 2 O 4 and ZnO, in conjunction with the elevated surface area, significantly contributed to the enhancement of photogenerated charge carrier separation and the augmentation of light absorption. Consequently, the nanocomposite exhibited a photocatalytic degradation efficiency of 93% for tetracycline in 45 minutes of visible light. The photodegradation pathway was further supported by LC-MS analysis, and ethanol scavenging tests confirmed the dominant role of hydroxyl radicals. The catalyst demonstrated high stability and reusability over five consecutive cycles with minimal loss of activity. These findings highlight the great potential of CoAl 2 O 4 @ZnO as a sustainable and efficient photocatalyst for the removal of antibiotic pollutants from wastewater. Declarations Author Contribution F. N.: Investigation, Implementation of experiments, Methodology, Manuscript preparation; H.Z.B.: Supervision, Validation, Manuscript preparation and revision; S.T.F.: Supervision, Validation, Conceptualization, Manuscript preparation and revision. Data Availability The datasets used and/or analyzed during the current study are available from the corresponding author on reasonable request. References Parvulescu, V. I., Epron, F., Garcia, H. & Granger, P. Recent progress and prospects in catalytic water treatment. Chem. Rev. 122 , 2981–3121 (2021). Ahmed, R. A. et al. 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Visible-light-induced mesoporous ZnO hexagonal sheets decorated by CuAl 2 O 4 nanoparticles for accelerating removal of tetracycline. Ceram. Int. 15 , 14092–14100 (2025). Zheng, X., Shen, Y., Zhou, Y., Wen, H. & Wen, J. Solar-light induced photocatalytic-persulfate activity of BiOCl 0.5 I 0.5 /NH 2 -MIL-88B (Fe) for tetracycline hydrochloride degradation. J. Water Process. Eng. 54 , 104034 (2023). Habibi, M. et al. Highly impressive activation of persulfate ions by novel ZnO/CuCo 2 O 4 nanostructures for photocatalytic removal of tetracycline hydrochloride under visible light. Environ. Technol. Innov. 24 , 102038 (2021). Habibi, M. et al. Visible-light-triggered persulfate activation by CuCo 2 S 4 modified ZnO photocatalyst for degradation of tetracycline hydrochloride. Colloids Surf. Physicochem Eng. Aspects . 642 , 128640 (2022). Peng, H., Ji, C., Yang, R., Dong, L. & Zheng, X. LaFeO 3 /MgFe 2 O 4 hybrids for boosting the solar-light photocatalytic persulfate oxidation of tetracycline hydrochloride. Colloids Surf. Physicochem Eng. Aspects , 134340 (2024). Peng, H., Li, H., Ye, B. & Zheng, X. Snowflake-like In 2 S 3 /Cu 2 S heterojunction for simultaneous photocatalytic persulfate oxidation of tetracycline hydrochloride and CO 2 photoreduction. Sep. Purif. Technol. 357 , 130242 (2025). Subhiksha, V. et al. Novel sandwich like interfacial engineering of Cu NPs on CuAl 2 O 4 anchored Bi 4 O5Br 2 nanoflower Z-scheme nano-heterojunction for enhanced photocatalytic degradation of doxycycline and tetracycline. J. Taiwan. Inst. Chem. Eng. 169 , 105952 (2025). Vinayagam, R. et al. Emerging contaminant removal using eco-friendly zinc ferrite nanoparticles: Sunlight-driven degradation of tetracycline. Emerg. Contaminants . 11 , 100469 (2025). Zheng, M., Gao, B., Sun, D., Wang, Y. & Gao, Y. Synergistic adsorption&photo-Fenton degradation of meloxicam and tetracycline by hollow nanoflower-like S-scheme FeWO 4 /ZnIn 2 S 4 heterojunction: Mechanism, toxicity assessment, and potential applications. Sep. Purif. Technol. 357 , 130122 (2025). Saranya, A. et al. Enhanced photocatalytic properties of visible light-responsive ZnS/FeWO 4 composites for degradation of tetracycline and Escherichia coli inactivation. J. Alloys Compd. 1010 , 176983 (2025). Zhao, M., Zhang, S., Shi, L. & Lei, C. Efficient photocatalytic degradation of tetracycline by Z-scheme ZnWO 4 /Bi 5 O 7 I heterojunction. Mater. Sci. Semicond. Process. 185 , 108935 (2025). Varghese, D. et al. Synergistic design of CuO/CoFe₂O₄/MWCNTs ternary nanocomposite for enhanced photocatalytic degradation of tetracycline under visible light. Sci. Rep. 15 , 320. 10.1038/s41598-024-82926-2 (2025). Additional Declarations No competing interests reported. Cite Share Download PDF Status: Published Journal Publication published 03 Jan, 2026 Read the published version in Scientific Reports → Version 1 posted Editorial decision: Revision requested 04 Jun, 2025 Reviews received at journal 14 May, 2025 Reviews received at journal 14 May, 2025 Reviewers agreed at journal 13 May, 2025 Reviewers agreed at journal 13 May, 2025 Reviewers invited by journal 13 May, 2025 Editor assigned by journal 13 May, 2025 Editor invited by journal 12 May, 2025 Submission checks completed at journal 10 May, 2025 First submitted to journal 23 Apr, 2025 You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. 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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-6515698","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":456207407,"identity":"39e50ea7-9913-4250-8da0-6914e4f50c0d","order_by":0,"name":"Farzaneh Nejadkhorasani","email":"","orcid":"","institution":"University of Isfahan","correspondingAuthor":false,"prefix":"","firstName":"Farzaneh","middleName":"","lastName":"Nejadkhorasani","suffix":""},{"id":456207408,"identity":"c3cd8f7e-2b79-43bd-afc7-1bf602327e93","order_by":1,"name":"Hassan Zali Boeini","email":"","orcid":"","institution":"University of Isfahan","correspondingAuthor":false,"prefix":"","firstName":"Hassan","middleName":"Zali","lastName":"Boeini","suffix":""},{"id":456207410,"identity":"0fc559f4-ce01-446f-b21e-fe5177acf74d","order_by":2,"name":"Saeid Taghavi Fardood","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA5UlEQVRIiWNgGAWjYLACxgYGBjb2xsYDCC5ewAzVwnOwgUQtDBIJDAeIcpN8A//Bj1932CX2ST5uOPAzh0Gev4G57QM+LQYHmJmlZc8kJ7ZJJzYc7N3GYDjjAGPzDLxagA6TlmxjNmYDajnAu42BcQMDYzMBhzEz/5ZsqzdmkzzYcPDvNgZ7gloYDjCzSX5sOyzHJsHYcBhoSyJBLQaHmc2sGduOy7HxJDYclt0mkTzjMCGHtTc+vvmzrZpHvv34w4dvt9nY9re3P8bvMGC0MPMguBJgEYKA8QcRikbBKBgFo2AEAwB1ckUqshVFUAAAAABJRU5ErkJggg==","orcid":"","institution":"Ilam University","correspondingAuthor":true,"prefix":"","firstName":"Saeid","middleName":"Taghavi","lastName":"Fardood","suffix":""}],"badges":[],"createdAt":"2025-04-23 22:38:07","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-6515698/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-6515698/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1038/s41598-025-33926-3","type":"published","date":"2026-01-03T15:57:38+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":82833169,"identity":"85d95259-ea29-46e8-bfbd-588962bfab64","added_by":"auto","created_at":"2025-05-15 17:57:08","extension":"jpg","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":35836,"visible":true,"origin":"","legend":"\u003cp\u003eChemical structure of Tetracycline.\u003c/p\u003e","description":"","filename":"Picture1.jpg","url":"https://assets-eu.researchsquare.com/files/rs-6515698/v1/86e672ebb48524418f8d2bcd.jpg"},{"id":82833168,"identity":"be2f22e7-3e0c-455b-822d-0caa8f64fbbe","added_by":"auto","created_at":"2025-05-15 17:57:08","extension":"jpg","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":76176,"visible":true,"origin":"","legend":"\u003cp\u003eXRD pattern of CoAl\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@ZnO NC.\u003c/p\u003e","description":"","filename":"Picture2.jpg","url":"https://assets-eu.researchsquare.com/files/rs-6515698/v1/cdf185fba8550003f22a8c75.jpg"},{"id":82834102,"identity":"500d55ed-541b-44f4-b648-92a7435e8bec","added_by":"auto","created_at":"2025-05-15 18:13:08","extension":"jpg","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":28585,"visible":true,"origin":"","legend":"\u003cp\u003eThe N\u003csub\u003e2\u003c/sub\u003e absorption/desorption isotherm of the CoAl\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@ZnO NC\u003cstrong\u003e.\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"Picture3.jpg","url":"https://assets-eu.researchsquare.com/files/rs-6515698/v1/6316967a4c7f630909beb6c7.jpg"},{"id":82833176,"identity":"ce0ca6ca-fe58-49a8-aca3-0e7fa3da4b0d","added_by":"auto","created_at":"2025-05-15 17:57:08","extension":"jpg","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":224320,"visible":true,"origin":"","legend":"\u003cp\u003eFESEM image (a) and TEM image (b) of CoAl\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@ZnO NC.\u003c/p\u003e","description":"","filename":"Picture4.jpg","url":"https://assets-eu.researchsquare.com/files/rs-6515698/v1/9d5ec39ace9054f25fbe1ab6.jpg"},{"id":82834101,"identity":"b620e9bb-3158-4245-bcd7-a881107068f6","added_by":"auto","created_at":"2025-05-15 18:13:08","extension":"jpg","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":23089,"visible":true,"origin":"","legend":"\u003cp\u003eEDX pattern of CoAl\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@ZnO NC.\u003c/p\u003e","description":"","filename":"Picture5.jpg","url":"https://assets-eu.researchsquare.com/files/rs-6515698/v1/0ff346bbabf59bba9e77ccd5.jpg"},{"id":82834383,"identity":"bc30b4ba-1fb0-4f64-ae58-c7e78b17792c","added_by":"auto","created_at":"2025-05-15 18:21:08","extension":"jpg","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":237678,"visible":true,"origin":"","legend":"\u003cp\u003eElement mapping images of CoAl\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@ZnO NC.\u003c/p\u003e","description":"","filename":"Picture6.jpg","url":"https://assets-eu.researchsquare.com/files/rs-6515698/v1/35f4edd6a06c71efc5a43afd.jpg"},{"id":82833177,"identity":"f534ade2-b169-4746-acdd-331113bf099b","added_by":"auto","created_at":"2025-05-15 17:57:08","extension":"jpg","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":28804,"visible":true,"origin":"","legend":"\u003cp\u003eTauc plot of CoAl\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@ZnO NC.\u003c/p\u003e","description":"","filename":"Picture7.jpg","url":"https://assets-eu.researchsquare.com/files/rs-6515698/v1/2fdc2f9e467f533f1b3b703c.jpg"},{"id":82833534,"identity":"7a1c37f7-1147-4005-a8e5-0517420338d6","added_by":"auto","created_at":"2025-05-15 18:05:08","extension":"jpg","order_by":8,"title":"Figure 8","display":"","copyAsset":false,"role":"figure","size":107331,"visible":true,"origin":"","legend":"\u003cp\u003e(a) Effect of visible light irradiation on TC degradation (b) Effect of CoAl\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@ZnO NC dosage (c) Effect of the initial concentration on the TC degradation efficiency (%) (d) UV-Vis spectra during TC degradation over time.\u003c/p\u003e","description":"","filename":"Picture8.jpg","url":"https://assets-eu.researchsquare.com/files/rs-6515698/v1/8ce428808d6bfe3f9003241e.jpg"},{"id":82833184,"identity":"26dc7ffc-357f-4355-af58-c141cd97fed3","added_by":"auto","created_at":"2025-05-15 17:57:08","extension":"jpg","order_by":9,"title":"Figure 9","display":"","copyAsset":false,"role":"figure","size":28869,"visible":true,"origin":"","legend":"\u003cp\u003eImpact of scavenging agents on TC degradation.\u003c/p\u003e","description":"","filename":"Picture9.jpg","url":"https://assets-eu.researchsquare.com/files/rs-6515698/v1/8659b651029c539b5bfa14c8.jpg"},{"id":82833174,"identity":"07b70c40-c3bd-4c61-a61e-1f5af5c7a820","added_by":"auto","created_at":"2025-05-15 17:57:08","extension":"jpg","order_by":10,"title":"Figure 10","display":"","copyAsset":false,"role":"figure","size":68835,"visible":true,"origin":"","legend":"\u003cp\u003eSuggested TC degradation pathways.\u003c/p\u003e","description":"","filename":"7.jpg","url":"https://assets-eu.researchsquare.com/files/rs-6515698/v1/d2051b4c3321ad5e56b6d67e.jpg"},{"id":82833527,"identity":"a7a1aad3-9dc3-44be-8a24-cfdeb60f5b02","added_by":"auto","created_at":"2025-05-15 18:05:08","extension":"jpg","order_by":11,"title":"Figure 11","display":"","copyAsset":false,"role":"figure","size":34987,"visible":true,"origin":"","legend":"\u003cp\u003eRecyclability of TC degradation over CoAl\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@ZnO NC.\u003c/p\u003e","description":"","filename":"11.jpg","url":"https://assets-eu.researchsquare.com/files/rs-6515698/v1/ac6e38b54c96e5a0aee24f2b.jpg"},{"id":99545269,"identity":"a75c6595-8eb2-4042-98a2-8df9935d4238","added_by":"auto","created_at":"2026-01-05 16:04:57","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":1841235,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-6515698/v1/3094b827-f695-4eb9-a80a-d678bc9a2535.pdf"}],"financialInterests":"No competing interests reported.","formattedTitle":"Green Synthesis of CoAl2O4@ZnO nanocomposite using Aamygdalus scoparia Spach gum and its photocatalytic activity for tetracycline degradation","fulltext":[{"header":"1. Introduction","content":"\u003cp\u003eThe increasing variety of water pollutants demands enhanced international attention to health and environmental safeguarding \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. A significant category comprises bioactive chemical residues from medical and hygiene consumer items. These pollutants are acknowledged as environmental hazards due to their potential physiological impacts on humans and other organisms, even at minimal concentrations \u003csup\u003e\u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e,\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e\u003c/sup\u003e. These chemical contaminants have become pervasive in the natural world as they are unable to be efficiently eliminated by traditional wastewater treatment processes due to their harmful effects and resistance to degradation \u003csup\u003e\u003cspan additionalcitationids=\"CR7\" citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e\u003c/sup\u003e. The elimination of these pollutants is of significant concern in health and safety management due to their potential detrimental impacts on humans and ecosystems. Modern oxidation technologies, particularly semiconductor-based photocatalysis, have acquired prominence for their removal due to their rapid degradation rates, cost-effectiveness, and mineralisation capabilities \u003csup\u003e\u003cspan additionalcitationids=\"CR10 CR11\" citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eFuture research on nanoparticles and nanomaterials needs environmentally friendly synthesis methods \u003csup\u003e\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e\u003c/sup\u003e. An eco-friendly strategy is defined as one that operates within the framework of green chemistry and green engineering to prevent the use and generation of harmful and undesirable substances, hence safeguarding the environment and living beings \u003csup\u003e\u003cspan additionalcitationids=\"CR15\" citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eSemiconductors with a wide bandgap, such as SnO\u003csub\u003e2\u003c/sub\u003e \u003csup\u003e17\u003c/sup\u003e, ZnO \u003csup\u003e\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e,\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e\u003c/sup\u003e and TiO\u003csub\u003e2\u003c/sub\u003e \u003csup\u003e20\u003c/sup\u003e, have been extensively investigated due to their excellent chemical stability and strong oxidizing ability under UV irradiation. Nonetheless, their significant bandgaps (Eg\u0026thinsp;\u0026gt;\u0026thinsp;3.0 eV) limit absorption to the ultraviolet spectrum, a minor part of solar radiation. This limitation significantly reduces their photocatalytic efficiency under visible light. Consequently, recent research has focused on modifying or combining them with narrow bandgap materials to enhance visible light absorption and improve photocatalytic performance. Many studies have concentrated on narrow band gap semiconductors, and spinels AB\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e are particularly fascinating owing to their chromatic characteristics and moderate conductivity \u003csup\u003e\u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e,\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e\u003c/sup\u003e. A is usually divalent, while B is a 3D metal \u003csup\u003e\u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e,\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e\u003c/sup\u003e. Spinels serve as catalyst supports due to their stability and strong resistance to acids and alkalis \u003csup\u003e\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e\u003c/sup\u003e. These materials are utilized for their unique optical and magnetic characteristics in various applications \u003csup\u003e\u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e,\u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e\u003c/sup\u003e. CoAl\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e features a spinel structure with distinct occupancy of aluminum and cobalt ions \u003csup\u003e\u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e\u003c/sup\u003e. This has motivated advancements in photodegradation via the integration of semiconductors with diverse bandgaps. Current investigations emphasize the creation of environmentally friendly, facilely synthesized, and lightweight materials \u003csup\u003e\u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e,\u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e\u003c/sup\u003e. The progression of photocatalytic materials exhibiting enhanced performance under natural conditions is critical. CoAl\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e and ZnO are noted for their high surface area and physicochemical stability, contributing to their improved photocatalytic efficiency due to successful electron-hole pair separation \u003csup\u003e\u003cspan additionalcitationids=\"CR32\" citationid=\"CR31\" class=\"CitationRef\"\u003e31\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eA sustainable sol\u0026ndash;gel technique was utilized for the synthesis of CoAl\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@ZnO nanocomposite. This eco-friendly synthesis method presents numerous benefits compared to traditional chemical approaches, such as ease of use, cost efficiency, safety, environmental suitability, and the removal of organic surfactants. The characteristics of the CoAl\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@ZnO NC were analyzed. This study is the first to document the photocatalytic degradation of tetracycline hydrochloride via CoAl\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@ZnO. The degradation of TC was assessed under varied conditions to identify optimal parameters such as nanocomposite dosage, initial TC concentration, light/dark settings, irradiation duration, and reusability. Figure\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e shows the chemical structures of Tetracycline (TC).\u003c/p\u003e \u003cp\u003e \u003c/p\u003e"},{"header":"2. Experimental","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003e2.1. Materials and characterization\u003c/h2\u003e \u003cp\u003eThe \u003cem\u003eAmygdalus scoparia Spach\u003c/em\u003e gum was collected from the Zagros Mountains in Ilam, Iran. Aluminium nitrate nonahydrate (Al(NO\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e3\u003c/sub\u003e\u0026middot;9H\u003csub\u003e2\u003c/sub\u003eO), cobalt(II) nitrate hexahydrate (Co(NO\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e\u0026middot;6H\u003csub\u003e2\u003c/sub\u003eO), and zinc nitrate hexahydrate (Zn(NO\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e\u0026middot;6H\u003csub\u003e2\u003c/sub\u003eO) were obtained from Merck Company. The XRD pattern of CoAl\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@ZnO NC was obtained by employing an X'Pert-PRO advanced diffractometer. The radiation source used was Cu-K, which has a wavelength of 1.5406 \u0026Aring;. The CoAl\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@ZnO NC was characterized using an EM 208S microscope for TEM and a Tescan Mira3 microscope for SEM, along with energy-dispersive X-ray (EDX) analysis and mapping. BET data analysis was conducted via a Belsorp Mini II, and UV-Vis absorption spectra were recorded using a UV-Vis spectrophotometer from the Cary series. The optical properties were analyzed via UV-Vis-DRS spectroscopy, utilizing the Jasco-V670. The band gap (Eg) was determined using Tauc's theory \u003csup\u003e\u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec4\" class=\"Section2\"\u003e \u003ch2\u003e2.2. Green synthesis of CoAl\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@ZnO\u003c/h2\u003e \u003cp\u003eFirstly, 0.4 g of the \u003cem\u003eAmygdalus scoparia Spach\u003c/em\u003e gum was dissolved in 50 mL of distilled water and agitated at 80\u0026deg;C for 30 minutes to produce a homogenous and translucent gel solution. Subsequently, 2 mmol of Al(NO\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e3\u003c/sub\u003e\u0026sdot;9H₂O and 1 mmol of Co(NO\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e\u0026middot;6H\u003csub\u003e2\u003c/sub\u003eO were added, and the mixture was stirred in a sand bath at 90\u0026deg;C for 12 h. The resulting precursor was then calcined at 600\u0026deg;C for 4 h to obtain CoAl\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e nanoparticles.\u003c/p\u003e \u003cp\u003eFor the synthesis of the CoAl\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@ZnO nanocomposite, the gel solution was freshly prepared using the same procedure. Then, 0.1 g of the synthesised CoAl\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e was dispersed into the gel and treated with ultrasonic irradiation for 4 minutes. Afterwards, 0.5 g of Zn(NO\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e\u0026middot;6H\u003csub\u003e2\u003c/sub\u003eO was added and the suspension was further sonicated for another 4 minutes. The mixture was subsequently stirred in a sand bath at 90\u0026deg;C for 12 hours. Finally, the obtained product was calcined at 500\u0026deg;C for 4 hours to form the CoAl\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@ZnO NC.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec5\" class=\"Section2\"\u003e \u003ch2\u003e2.3. Photocatalytic experiment\u003c/h2\u003e \u003cp\u003ePhotodegradation experiments were performed under visible light irradiation inside a box with an 80 W fluorescent lamp (λ\u0026thinsp;\u0026gt;\u0026thinsp;400 nm). The photocatalytic efficacy of the CoAl\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@ZnO nanocomposite was assessed through the degradation of tetracycline (TC) in aqueous solution under ambient conditions. A 50 mL TC solution was employed to ascertain optimal degradation efficiency, while evaluating different factors including CoAl\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@ZnO dosage, initial TC concentration, reaction time, light versus dark conditions, and catalyst reusability. The degradation efficiency of TC was analyzed via UV\u0026ndash;Vis spectroscopy at λ_max\u0026thinsp;=\u0026thinsp;371 nm. The following formula was employed to determine the degradation rate of TC.\u003cdiv id=\"Equa\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equa\" name=\"EquationSource\"\u003e\n$$\\:\\text{D}\\text{e}\\text{g}\\text{r}\\text{a}\\text{d}\\text{a}\\text{t}\\text{i}\\text{o}\\text{n}=\\frac{\\left({A}_{0}-{A}_{t}\\right)}{{A}_{0}}\\times\\:100$$\u003c/div\u003e\u003c/div\u003e\u003c/p\u003e \u003cp\u003eThe initial and ultimate absorption at time t\u003csub\u003e0\u003c/sub\u003e and t min are denoted by the symbols A\u003csub\u003e0\u003c/sub\u003e and A\u003csub\u003et\u003c/sub\u003e, respectively.\u003c/p\u003e \u003c/div\u003e"},{"header":"3. Result and discussion","content":"\u003cdiv id=\"Sec7\" class=\"Section2\"\u003e \u003ch2\u003e3.1. Characterization\u003c/h2\u003e \u003cp\u003eXRD analysis was conducted to elucidate the structural characteristics, phases, and crystallite size of the synthesized nanocomposite. The XRD pattern of CoAl\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@ZnO NC is shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e. The XRD pattern of ZnO contains distinctive peaks at 31.95\u0026deg;, 34.66\u0026deg;, 36.47\u0026deg;, 47.72\u0026deg;, 56.75\u0026deg;, 63.10\u0026deg;, 66.49\u0026deg;, 68.16\u0026deg;, 69.17\u0026deg;, 72.72\u0026deg;, and 77.33\u0026deg;, which are associated with the (100), (002), (101), (102), (110), (103), (200), (112), (201), (004), and (202) planes, respectively and match well with pure ZnO (JCPDS 79\u0026ndash;0205). The XRD pattern of CoAl\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e (JCPDS card no. 44\u0026ndash;0160) exhibits peaks at 31.40\u0026deg;, 37.01\u0026deg;, 45.04\u0026deg;, 55.82\u0026deg;, 59.46\u0026deg;, 65.39\u0026deg;, 74.62\u0026deg;, and 77.33\u0026deg;, corresponding to the (220), (311), (400), (422), (511), (440), (620), and (533) planes, respectively, consistent with pure CoAl\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e (JCPDS 03-0896). The crystallite size of the CoAl\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@ZnO nanocomposite, estimated using the Scherrer Eq.\u0026nbsp;3\u003csup\u003e5\u003c/sup\u003e, was found to be approximately 11 nm.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe active surface area of the synthesized nanocomposite was assessed using BET. The findings indicate that the nanoparticles possess a specific surface area of 40.045 m\u0026sup2;g\u003csup\u003e-\u003c/sup\u003e\u0026sup1;, a pore width of 21.048 nm, and a total pore volume of 0.2107 cm\u0026sup3;g\u003csup\u003e-\u003c/sup\u003e\u0026sup1;. Figure\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e depicts the nitrogen adsorption-desorption isotherm, which, according to the IUPAC classification, shows a typical type IV isotherm with H3 hysteresis loops, indicative of mesoporous materials \u003csup\u003e\u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e36\u003c/span\u003e\u003c/sup\u003e. The mesoporous CoAl\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@ZnO nanocomposites enhance photocatalytic degradation of tetracycline by increasing surface area and light absorption.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eFigure\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ea shows the SEM image of the CoAl\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@ZnO nanocomposite, which exhibits a homogeneous and spherical shape. The TEM image further confirms the synthesis of the CoAl\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@ZnO nanocomposite, revealing a uniform particle distribution and spherical morphology, with an average size of approximately 25\u0026thinsp;\u0026minus;\u0026thinsp;30 nm (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003eb).\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe EDS analysis of the CoAl\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@ZnO nanocomposite Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e reveals the presence of the component elements (Zn, Al, Co, O). Figure\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003e shows the EDX mapping of the CoAl\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@ZnO nanocomposites, confirming the spatial distribution of Zn, Co, Al, and O within the sample.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eDRS was performed to examine the optical characteristics of the produced nanocomposite. The band gap of the CoAl\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@ZnO NC was determined using the Tauc equation. The Tauc plot of the nanocomposite is illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003e. The nanocomposite exhibited a band gap energy of 3 eV. Thus, the reduced band gap indicates that the CoAl\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@ZnO NC can be activated with lower photon energy under visible light \u003csup\u003e\u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e37\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec8\" class=\"Section2\"\u003e \u003ch2\u003e3.2. Photodegradation of TC using CoAl₂O₄@ZnO NC\u003c/h2\u003e \u003cp\u003eThe degradation of TC was carried out using the CoAl\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@ZnO photocatalyst under visible light irradiation. The processes evaluated include adsorption (nanocomposite in darkness), photolysis, and photocatalysis. Figure\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e8\u003c/span\u003ea shows that the degradation efficiencies for adsorption, photolysis, and photocatalysis were 47%, 0%, and 93%, respectively, within 45 minutes.\u003c/p\u003e \u003cp\u003eThe efficiency of TC photodegradation and photocatalytic activity depends on the optimized usage of the CoAl\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@ZnO nanocomposite. Figure\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e8\u003c/span\u003eb illustrates the effect of catalyst loading (0.02\u0026ndash;0.05 g) on tetracycline degradation. Over 45 minutes, the photocatalytic efficiency increased as the catalyst loading rose from 0.02 g to 0.04 g, due to the availability of more active reaction sites. However, when the loading exceeded 0.04 g, the efficiency dropped to 90%, attributed to nanocomposite agglomeration and increased particle collisions. These phenomena led to greater light scattering and reduced light penetration, despite the increase in active sites \u003csup\u003e\u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e38\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eThe effect of varying initial concentrations of TC on the photodegradation efficiency was investigated in the range of 10\u0026ndash;30 mg/L, while other parameters remained constant (0.04 g photocatalyst, 45 min). As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e8\u003c/span\u003ec, TC degradation efficiency decreases as the initial concentration increases. This may be ascribed to decreased photon penetration to the photocatalyst surface and reduced generation of free radicals \u003csup\u003e\u003cspan citationid=\"CR39\" class=\"CitationRef\"\u003e39\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eThe experiment determined the optimal duration for dye degradation by utilizing the optimal catalyst dose and TC concentration across various irradiation times, with findings presented in Fig.\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e8\u003c/span\u003ed. The λ\u003csub\u003emax\u003c/sub\u003e of TC occurs at 371 nm, and degradation efficacy is evidenced by a reduction in maximum absorbance as irradiation time increases. It is evident that 93% of TC was degraded within 45 minutes.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eScavenger trapping studies were performed to clarify the roles of reactive species in TC photodegradation \u003csup\u003e\u003cspan additionalcitationids=\"CR41\" citationid=\"CR40\" class=\"CitationRef\"\u003e40\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR42\" class=\"CitationRef\"\u003e42\u003c/span\u003e\u003c/sup\u003e. As illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig9\" class=\"InternalRef\"\u003e9\u003c/span\u003e, the addition of ethanol, a recognized \u003cb\u003e\u0026middot;\u003c/b\u003eOH scavenger, significantly reduced the degradation efficiency to 43%, signifying that \u003cb\u003e\u0026middot;\u003c/b\u003eOH radicals are the dominant species in the degradation process. The presence of EDTA (h⁺ scavenger) and AgNO₃ (e⁻ scavenger) reduced the degradation efficiency to 78% and 85%, respectively, suggesting that holes and electrons contribute to a lesser extent. Super oxide radicals played a minimal role in the process because the introduction of O₂\u0026bull;⁻ scavenger p-benzoquinone only caused a minor efficiency change. Therefore, the photocatalytic degradation of TC is primarily governed by \u0026bull;OH-mediated mechanisms, with electrons and holes acting as secondary participants.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe photodegradation by-products of tetracycline (TC) in the presence of CoAl\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@ZnO NC were identified by employing LC-MS analysis under optimized experimental conditions. Figure\u0026nbsp;\u003cspan refid=\"Fig10\" class=\"InternalRef\"\u003e10\u003c/span\u003e illustrates the degradation pathways of TC as detected by LC-MS. The photocatalytic activity of CoAl\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@ZnO NC facilitates the generation of hydroxyl radicals (\u0026bull;OH) under visible light. The excitation of electrons generates electron-hole pairs that oxidize water, resulting in the formation of \u0026bull;OH radicals that decompose tetracycline. These radicals interact with TC molecules, promoting their degradation. The LC-MS results indicate that the TC molecular structure decomposes, yielding numerous intermediate compounds during photodegradation. Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e presents these products along with their degradation intermediates. Studies indicate that the nanocomposite enhances the generation of reactive species, such as \u0026bull;OH radicals, which promote the degradation of the TC molecule via oxidation reactions. The findings offer critical insights into the tetracycline (TC) degradation mechanism and the prospective applications of CoAl\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@ZnO NC in wastewater treatment contexts \u003csup\u003e\u003cspan additionalcitationids=\"CR44 CR45\" citationid=\"CR43\" class=\"CitationRef\"\u003e43\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR46\" class=\"CitationRef\"\u003e46\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab1\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 1\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eLC-MS Detection of TC Degradation Products.\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"6\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eNo\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eStructure\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003em/z\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eNo\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eStructure\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c6\"\u003e \u003cp\u003em/z\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e\u003cb\u003e358\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e\u003cb\u003e276\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e\u003cb\u003e260\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e\u003cb\u003e208\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e\u003cb\u003e192\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e6\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e\u003cb\u003e118\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e7\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e\u003cb\u003e104\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e8\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e\u003cb\u003e86\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003eAn essential benefit of employing nanocomposite in aqueous purification is their capability to be utilized repeatedly \u003csup\u003e\u003cspan citationid=\"CR47\" class=\"CitationRef\"\u003e47\u003c/span\u003e\u003c/sup\u003e. The stability and photocatalytic efficacy of CoAl\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@ZnO NC was examined in five successive experiments under the optimal conditions. The nanocomposite from each experiment was subjected to centrifugation, washed with distilled water, and reutilized to evaluate its reusability. The results, as depicted in Fig.\u0026nbsp;\u003cspan refid=\"Fig11\" class=\"InternalRef\"\u003e11\u003c/span\u003e, demonstrated a minimal reduction in degradation efficiency even after five cycles of regeneration.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe photocatalytic effectiveness of CoAl\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@ZnO NC was assessed against previously documented photocatalysts. Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e demonstrates that the synthesized composite exhibited substantial TC degradation efficiency, establishing it as a plausible candidate for wastewater remediation. The enhanced photocatalytic efficacy of the CoAl\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@ZnO NC is primarily due to the increased surface area and the synergistic interaction between ZnO and CoAl\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e, which together enhance light absorption and facilitate efficient charge carrier separation.\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab2\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 2\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003ePhotocatalytic performance comparison of CoAl\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@ZnO with other photocatalysts\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"7\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c7\" colnum=\"7\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003ePhotocatalysts\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eSynthesis method\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eLight source\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eTC conc. (ppm)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eTime/ min\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c6\"\u003e \u003cp\u003eRemoval efficiency\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c7\"\u003e \u003cp\u003eRef\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eCuAl\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e/ZnO\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eHydrothermal\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eXe lamp,300 W\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e20\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e90\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e100\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e\u003csup\u003e\u003cspan citationid=\"CR48\" class=\"CitationRef\"\u003e48\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eBiOCl\u003csub\u003e0.5\u003c/sub\u003eI\u003csub\u003e0.5\u003c/sub\u003e/NH\u003csub\u003e2\u003c/sub\u003e-MIL-88B(Fe)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eXe lamp, 300 W\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e120\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e120\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e91.15\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e\u003csup\u003e\u003cspan citationid=\"CR49\" class=\"CitationRef\"\u003e49\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eZnO/CuCo\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eHydrothermal\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eLED lamp, 50 W\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e6.7\u0026times;10\u003csup\u003e\u0026minus;\u0026thinsp;5\u003c/sup\u003e mol L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e60\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e100\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e\u003csup\u003e\u003cspan citationid=\"CR50\" class=\"CitationRef\"\u003e50\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eZnO/CuCo\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e4\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eHydrothermal\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eXe lamp, 300W\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e6.7\u0026times;10\u003csup\u003e\u0026minus;\u0026thinsp;5\u003c/sup\u003e mol L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e80\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e100\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e\u003csup\u003e\u003cspan citationid=\"CR51\" class=\"CitationRef\"\u003e51\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eLaFeO\u003csub\u003e3\u003c/sub\u003e/MgFe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eSol-gel\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eXe lamp, 300 W\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e300\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e120\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e97.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e\u003csup\u003e\u003cspan citationid=\"CR52\" class=\"CitationRef\"\u003e52\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e3-In\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e3\u003c/sub\u003e/Cu\u003csub\u003e2\u003c/sub\u003eS\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eHydrothermal\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eXe lamp, 300W\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e120\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e150\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e99.90\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e\u003csup\u003e\u003cspan citationid=\"CR53\" class=\"CitationRef\"\u003e53\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eCuAl\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e-Cu-Bi\u003csub\u003e4\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003eBr\u003csub\u003e2\u003c/sub\u003e (CCB NCs)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eUltrasonication-assisted coprecipitation\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eHalogen Lamp, 500 W\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e75\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e160\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e95.4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e\u003csup\u003e\u003cspan citationid=\"CR54\" class=\"CitationRef\"\u003e54\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eZnFe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eGreen hydrothermal\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e10\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e180\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e94.12\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e\u003csup\u003e\u003cspan citationid=\"CR55\" class=\"CitationRef\"\u003e55\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eFeWO\u003csub\u003e4\u003c/sub\u003e/ZnIn\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e4\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eSolvothermal\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003exenon lamp (500 W\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e60\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e60\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e92.90\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e\u003csup\u003e\u003cspan citationid=\"CR56\" class=\"CitationRef\"\u003e56\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eZnS/FeWO\u003csub\u003e4\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eHydrothermal\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e10\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e105\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e91.70\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e\u003csup\u003e\u003cspan citationid=\"CR57\" class=\"CitationRef\"\u003e57\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eZ-scheme ZnWO\u003csub\u003e4\u003c/sub\u003e/ Bi\u003csub\u003e5\u003c/sub\u003eO7I\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eHydrothermal\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eXe lamp, 300W\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e20\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e60\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e96.80\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e\u003csup\u003e\u003cspan citationid=\"CR58\" class=\"CitationRef\"\u003e58\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eCuO/CoFe₂O₄/MWCNTs\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eHydrothermal\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eXe lamp, 150 W\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e120\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e98.1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e\u003csup\u003e\u003cspan citationid=\"CR59\" class=\"CitationRef\"\u003e59\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eCoAl\u003c/b\u003e\u003csub\u003e\u003cb\u003e2\u003c/b\u003e\u003c/sub\u003e\u003cb\u003eO\u003c/b\u003e\u003csub\u003e\u003cb\u003e4\u003c/b\u003e\u003c/sub\u003e\u003cb\u003e/ZnO\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e\u003cb\u003eGreen sol-gel\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e\u003cb\u003efluorescent lamp, 80W\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e\u003cb\u003e20\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e\u003cb\u003e45\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e\u003cb\u003e93\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003eThis work\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003c/div\u003e"},{"header":"4. Conclusions","content":"\u003cp\u003eIn this study, a CoAl\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@ZnO nanocomposite was synthesized via a green sol\u0026ndash;gel method using \u003cem\u003eAmygdalus scoparia Spach\u003c/em\u003e gum as a natural stabilizing agent. Structural, morphological and surface characterizations, including BET, SEM and DRS analysis confirmed the formation of a porous, spherical nanocomposite with a specific surface area of 40.045 m\u0026sup2;/g and a band gap of 3.0 eV, enabling efficient activation under visible light. The synergistic interaction between CoAl\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e and ZnO, in conjunction with the elevated surface area, significantly contributed to the enhancement of photogenerated charge carrier separation and the augmentation of light absorption. Consequently, the nanocomposite exhibited a photocatalytic degradation efficiency of 93% for tetracycline in 45 minutes of visible light. The photodegradation pathway was further supported by LC-MS analysis, and ethanol scavenging tests confirmed the dominant role of hydroxyl radicals. The catalyst demonstrated high stability and reusability over five consecutive cycles with minimal loss of activity. These findings highlight the great potential of CoAl\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@ZnO as a sustainable and efficient photocatalyst for the removal of antibiotic pollutants from wastewater.\u003c/p\u003e"},{"header":"Declarations","content":"\u003ch2\u003eAuthor Contribution\u003c/h2\u003e\u003cp\u003eF. N.: Investigation, Implementation of experiments, Methodology, Manuscript preparation; H.Z.B.: Supervision, Validation, Manuscript preparation and revision; S.T.F.: Supervision, Validation, Conceptualization, Manuscript preparation and revision.\u003c/p\u003e\u003ch2\u003eData Availability\u003c/h2\u003e\u003cp\u003eThe datasets used and/or analyzed during the current study are available from the corresponding author on reasonable request.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eParvulescu, V. I., Epron, F., Garcia, H. \u0026amp; Granger, P. Recent progress and prospects in catalytic water treatment. \u003cem\u003eChem. Rev.\u003c/em\u003e \u003cb\u003e122\u003c/b\u003e, 2981\u0026ndash;3121 (2021).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eAhmed, R. A. et al. 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Rep.\u003c/em\u003e \u003cb\u003e15\u003c/b\u003e, 320. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003e10.1038/s41598-024-82926-2\u003c/span\u003e\u003cspan address=\"10.1038/s41598-024-82926-2\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e (2025).\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"scientific-reports","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"scirep","sideBox":"Learn more about [Scientific Reports](http://www.nature.com/srep/)","snPcode":"","submissionUrl":"","title":"Scientific Reports","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"Scientific Reports","inReviewEnabled":true,"inReviewRevisionsEnabled":true},"keywords":"Green synthesis, Tetracycline Degradation, photocatalytic activity, Nanocomposite","lastPublishedDoi":"10.21203/rs.3.rs-6515698/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-6515698/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eA novel CoAl\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@ZnO nanocomposite (NC) was synthesized via a green, low-cost, and simple sol-gel method using \u003cem\u003eAmygdalus scoparia Spach\u003c/em\u003e gum. The photocatalytic efficacy of the produced CoAl\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@ZnO NC was examined for the degradation of tetracycline (TC) under visible light. The CoAl\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@ZnO NC analyzed using XRD, BET, UV-Vis-DRS, FESEM, TEM, EDX and Mapping. The XRD analysis confirmed the formation of CoAl\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e with a cubic spinel structure and ZnO with a hexagonal wurtzite structure. BET analysis revealed a specific surface area of approximately 40.045 m\u003csup\u003e2\u003c/sup\u003e/g. The band gap energy was estimated to be around 3.0 eV using the Tauc equation.\u003c/p\u003e \u003cp\u003eThe CoAl\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e@ZnO NC demonstrated significant photocatalytic efficacy, obtaining 93% degradation of tetracycline in 45 min under visible light irradiation. LC-MS analysis identified multiple intermediate products during the comprehensive investigation of the photodegradation mechanism which confirmed the degradation pathway. The addition of ethanol as a scavenger led to reduced photocatalytic activity which demonstrates that hydroxyl radicals (\u0026bull;OH) play a crucial role in the degradation process. The nanocomposite maintained stability and photocatalytic efficiency throughout five repeated tests which showed minimal reduction in activity.\u003c/p\u003e","manuscriptTitle":"Green Synthesis of CoAl2O4@ZnO nanocomposite using Aamygdalus scoparia Spach gum and its photocatalytic activity for tetracycline degradation","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-05-15 17:57:03","doi":"10.21203/rs.3.rs-6515698/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Revision requested","date":"2025-06-04T09:09:43+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-05-14T23:20:21+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-05-14T06:23:23+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"105115106867485468488583158267248887226","date":"2025-05-14T00:32:08+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"3712625366930368628463032213462486985","date":"2025-05-13T20:00:51+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2025-05-13T04:11:43+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2025-05-13T04:04:25+00:00","index":"","fulltext":""},{"type":"editorInvited","content":"","date":"2025-05-12T17:53:01+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2025-05-10T16:10:22+00:00","index":"","fulltext":""},{"type":"submitted","content":"Scientific Reports","date":"2025-04-23T22:22:23+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"scientific-reports","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"scirep","sideBox":"Learn more about [Scientific Reports](http://www.nature.com/srep/)","snPcode":"","submissionUrl":"","title":"Scientific Reports","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"Scientific Reports","inReviewEnabled":true,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"f09c08a9-3522-4d4a-85d0-c72b4746c244","owner":[],"postedDate":"May 15th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[{"id":48492662,"name":"Physical sciences/Chemistry/Biosynthesis"},{"id":48492663,"name":"Physical sciences/Chemistry/Catalysis/Photocatalysis"}],"tags":[],"updatedAt":"2026-01-05T16:00:18+00:00","versionOfRecord":{"articleIdentity":"rs-6515698","link":"https://doi.org/10.1038/s41598-025-33926-3","journal":{"identity":"scientific-reports","isVorOnly":false,"title":"Scientific Reports"},"publishedOn":"2026-01-03 15:57:38","publishedOnDateReadable":"January 3rd, 2026"},"versionCreatedAt":"2025-05-15 17:57:03","video":"","vorDoi":"10.1038/s41598-025-33926-3","vorDoiUrl":"https://doi.org/10.1038/s41598-025-33926-3","workflowStages":[]},"version":"v1","identity":"rs-6515698","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-6515698","identity":"rs-6515698","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}