Study of sorption properties of zirconia, alumina and silica in relation to repellents

Study of sorption properties of zirconia, alumina and silica in relation to repellents | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article Study of sorption properties of zirconia, alumina and silica in relation to repellents Sergei A. Zverev, Yana V. Vinogradova, Anna A. Selivanova, Roman D. Solovov, and 3 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-3972861/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 16 May, 2024 Read the published version in Colloid and Polymer Science → Version 1 posted 7 You are reading this latest preprint version Abstract In this work, the morphology of zirconia, alumina, and silicas was studied and static sorption of the repellents N,N-diethyl-3-methylbenzamide and ethyl-3-[acetyl(butyl)amino]propionate on these oxides was carried out. ZrO2, Al2O3, SiO2 phenyl were shown to have high sorption activity to the repellents N,N-diethyl-3-methylbenzamide (239 mg/g for SiO2 phenyl) and ethyl-3-[acetyl(butyl)amino]propionate (251 mg/g for ZrO2). Pointedly, it was found that despite having the largest pore volume and high specific surface area (compared to the other studied oxides), SiO2 C2 has a significantly inferior sorption capacity in respect to other oxides, in particular SiO2 phenyl, which can be explained by the presence of the phenyl group in the latter that has chemical affinity for repellent molecules. Obtained isotherms of SiO2 300 also confirm the low sorption activity towards N,N-diethyl-3-methylbenzamide. The sorption equilibrium for both repellents, in most cases, is described by the Langmuir monomolecular adsorption model. The obtained results suggest that the studied zirconia, alumina, and silica can be used as carrier components of repellents. Sorption Alumina Zirconia Silica Repellents Isothermal models Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Introduction Climate changes in the past decades have led to a significant increase in the number of various diseases caused by bloodsucking arthropods [ 1 – 4 ]. According to the World Health Organization (WHO), due to the climate changes in 2030–2050, the malaria mortality rate may increase to 250 000 cases. [ 5 ]. In particular, this can be explained by the fact that the mosquitoes are able to quickly adapt to the environmental changes, which leads to their fast reproduction and migration in the settings of higher temperatures and wet climate [ 1 ]. Bloodsucking arthropods are the cause of disease in more than 700 million people yearly, with every 17th case leading to death [ 6 ]. To protect people and prevent the spreading of virulent diseases, products and materials with repellent properties are widely used. N,N -diethyl-3-methylbenzamide (DEET), N,N -diethylphenylacetamide (DEEPA), ethyl 3-[acetyl(butyl)amino]propionate (IR3535) and icaridin (KBR 3023) are considered the classical synthetic repellents [ 3 , 7 ]. These compounds are able to effectively repel mosquitoes and some other bloodsucking arthropods. However, their use typically implies applying the compounds directly onto the skin, which may cause irritation and allergy. Moreover, it is known that DEET is able to diffuse through the layers of skin and reach the bloodstream [ 3 ]. On the other hand, natural repellants based on citronella, geranium, lantana, etc. essential oils are widely used as well. Agents based on them have low toxicity, thus less prominent side effects; however, they are noted to have lower repellent activity [ 7 ]. Searching for new compounds and novel approaches to ensure the epidemiological welfare of the population is becoming the growing tendency among modern research [ 1 – 3 , 6 , 8 – 10 ]. One of those directions is developing materials for manufacturing special protective clothing with insecticide and repellent properties [ 11 ]. E.g., sol-gel technology allows obtaining textile, coated with silica nanoparticles impregnated with permethrin [ 12 ]. Such coating allows ensuring a high level of protection from insect bites without losing its physical properties. Moreover, textile obtained through sol-gel technique are stable in regards to environmental exposure, which is confirmed by the intact efficacy of the insecticide-impregnated textile after washing. To endow the materials with required properties, a method of sorption of active substances on the surface of sorbents is also used. For example, pesticides, repellents and herbicides sorption on organic sorbents have been studied extensively in modern literature, however, most of the studies are dedicated to the problem of wastewater and soil treatment for pollutants removal [ 13 – 16 ]. Study results show that inorganic compounds, such as activated charcoal and other allotropic modification of carbon, silicon oxides and metal oxides are able to selectively sorb on their surface, required compounds with high efficiency. However, these properties of the inorganic compounds are suitable for implementation not only in wastewater treatment system but also in other areas, namely designing of material with specific properties. It is known that synthesized ZrO 2 and Al 2 O 3 possess high sorption properties [ 17 – 26 ]. Their unique properties, such as large surface area, large pore volume, high porosity, high physical and chemical stability, make them stand out among other sorbents [ 17 ]. Due to a presence of acid and basic centers on their surface, aluminium and zirconium oxides have affinity for representatives of various substances classes, e.g., compounds of uranium, chromium(VI), yttrium(III), etc., which allows selective sorption of compounds of these metals from different objects [ 17 , 21 – 25 ]. An important feature of this kind of research is the study of kinetic and isothermal parameters as they make it possible to describe the characteristics of the mass transfer process of substances. Calculated characteristics allow us not only to analyze the data on sorption diffuse parameters but also to increase the adsorption capacity of developed materials. In this work, the sorption capacity of aluminium, zirconium and silicon oxides with functional groups for DEET and IR3535 repellents was studied; thermodynamic parameters of sorption were calculated and potential application of the obtained composite compounds as an active component of materials with repellent properties was evaluated. Experimental Materials N,N -diethyl-3-methylbenzamide (DEET) was purchased from Sigma Aldrich (USA); ethyl 3-[acetyl(butyl)amino] propionate (IR3535) was purchased from Merck KGaA (Darmstadt, Germany); acetonitrile was purchased from Honeywell (Charlotte, North Carolina, USA); aluminum nitrate nonahydrate, zirconyl nitrate dihydrate, ammonium nitrate, citric acid hydrate and ethylene glycol used were from JSC LenReactiv (St. Petersburg, Russia); Silasorb С2 (SiO 2 C2), Silasorb phenyl (SiO 2 phenyl), Silasorb 300 (SiO 2 300) used were from Elsico (Moscow, Russia). All other reagents were analytical grade or higher and used without further purification. Methods Synthesis of ZrO 2 and Al 2 O 3 ZrO 2 synthesis was carried out according to the following technique. 49 g of 0.97 mol/L zirconyl nitrate solution was dissolved in deionized water in a 1000 cm 3 glass beaker, then 197 g of ammonium nitrate was added. The beaker was placed on a hotplate with controlled heating, and the solution was gradually heated to 80°C for two hours while constantly stirred. Thirty minutes after the dissolution of the salts, 38 g of citric acid was added. After reaching 80°C, the temperature of the solution was gradually increased at a rate of 5–7°C/h. Two hours after the dissolution of citric acid, 11 g of ethylene glycol was added, and the temperature was increased to 95°C. When the solution was evaporated to a viscous paste, it was transferred to an evaporation bowl and placed in a steel enameled container and exposed to further heating up to 800 ℃. During the synthesis, a blackish-gray powder with a distinctive coral-shaped structure was formed. The obtained product containing zirconium oxide was calcined in the air at 800°C for no less than 2 hours. The synthesis and heat treatment of aluminium oxide was carried out in the similar fashion. To achieve the desired results, 7 g of aluminium nitrate, 230 g of ammonium nitrate, 45 g of citric acid and 13 g of ethylene glycol were used. The average yield for both products was found to be around 96%. Scanning Electron Microscopy (SEM) Morphology of the oxide samples was studied on SUPRA 55 Field Emission Scanning Electron Microscope (Carl Zeiss, Oberkochen, Germany) using an SE2 detector under 1kV accelerating voltage. Analysis of specific surface area of the oxides according to the Brunauer–Emmett–Teller theory The specific surface area and pore volume of the oxide samples were calculated using the Brunauer–Emmett–Teller method, with the experiments being performed on a Beckman Coulter SA 3100 analyzer (Indianapolis, US). Static sorption of DEET and IR3535 DEET and IR3535 isothermal sorption process was carried out by mixing 100 mg of zirconia, alumina or silica with repellent solutions (C solutions = 100–1000 mg/L) in 40 ml of acetonitrile for 120 min at 24 ± 1°C. To determine changes in the concentration of repellent solutions, samples were collected after 5, 15, 30, 60, 120, and 360 min and filtered through 0.45 µm PTFE filter. The optical density of DEET and IR3535 in the analyzed samples was recorded on a Varian Cary 50 UV-Vis spectrophotometer (Utah, USA) in the spectral range of 190–210 nm. Concentrations of DEET and IR3535 in the samples were calculated using absolute calibration method. The DEET and IR3535 repellent solutions that were used to plot the calibration curves were prepared by dilution the stock solution. Stock solution was prepared by accurately measuring the necessary amount of the compound to an approximation of the fourth decimal number, and diluting it in acetonitrile. Results and discussion Alumina, zirconia and silica were chosen as potential repellent carrier substances as inorganic compounds with high sorption capacity as a result of searching for new way to produce repellent materials. To obtain compounds with high porous surface area, ZrO 2 and Al 2 O 3 were synthesized using the glycol-citrate method. This method allows obtaining porous metal oxides with desired structural characteristics and low content of by-products [ 27 ]. SiO 2 phenyl, SiO 2 C2, SiO 2 300 were commercially purchased and used without purification. Choosing silica is explained by their various properties provided due to the presence of functional groups: SiO 2 300 contains no functional groups and is hydrophilic; SiO 2 C2 contains alkyl radicals; SiO 2 phenyl contains phenyl groups that may provide additional affinity for DEET and IR3535 through interaction of the π-system with the amino groups of the repellents. SEM and BET methods were used to study the morphology and sorption characteristics of the obtained oxides. Data analysis showed that the combination of these methods allows us to evaluate the possibility of using these oxides as carrier sorbents. Scanning Electron Microscopy (SEM) SEM results analysis shows that zirconium (A) and aluminum (B) oxides posses a distinct lamellar structure with a thickness of 40–50 nm, which is an inherent trait of substances obtained by the glycol-citrate synthesis method (Fig. 1 ). The inner porous structure is also clearly visible, which can imply the existence of potential sorption centers. SiO 2 phenyl (C) and SiO 2 C2 (D) possess asymmetrical cubic shape with different structural irregularities. SiO 2 300 (E) has a structure consisting of densely packed spherical objects with an average diameter of 10 µm. Silica, like zirconia and alumina, has a prominent porous structure, which allows assuming their high sorption properties. Brunauer–Emmett–Teller (BET) theory BET method, consisting of the low-temperature nitrogen adsorption-desorption process on the surface of the studied samples, was used to calculate the specific surface area of porous zirconium, aluminum, and silicon oxides (Fig. 2 ). The Barrett-Joyner-Halenda (BJH) method was used to calculate the pore size distribution and determine the average pore size [ 28 ]. The parameters of the porous structure of the samples are presented in Table 1 . Table 1 Porosity parameters of zirconium, aluminum, SiO 2 phenyl, SiO 2 C2, and SiO 2 300 oxides calculated using the BJH method. Sorbent Specific surface area, m 2 /g Monolayer volume, cc/g Average pore volume, cc/g Average pore size, nm ZrO 2 34.3 ± 1.7 7.88 ± 0.39 0.0865 ± 0.0043 46.0 ± 2.3 Al 2 O 3 85.5 ± 4.3 19.6 ± 1.0 0.119 ± 0.006 3.84 ± 0.19 SiO 2 phenyl 211 ± 11 48.4 ± 2.4 0.161 ± 0.008 9.85 ± 0.49 SiO 2 C2 380 ± 19 87.3 ± 4.4 0.306 ± 0.015 3.84 ± 0.19 SiO 2 300 273 ± 14 62.7 ± 3.1 0.304 ± 0.015 13.8 ± 0.7 The presented BET isotherms show that when the value of relative pressure P s /P 0 is less than 1, the nitrogen adsorption capacity increases rapidly for all oxides, which indicates the mesoporous structure of the studied compounds (Fig. 2 ). When the value of relative pressure P s /P 0 is more than 0.4, a hysteresis loop is observed for all curves, indicating the formation of capillary condensation for all oxides. Data analysis of the specific surface area and pore sizes calculations of the studied oxides showed that silicon oxides SiO 2 C2, SiO 2 300 and SiO 2 phenyl (211 ÷ 380 m 2 /g) have a larger area compared to synthetic zirconium and aluminum oxides (34.3 and 85.5 m 2 /g, respectively). The obtained data also shows a significant difference in pore size for each of the oxides. ZrO 2 has pores of around 46.0 nm in size, indicating its mesoporous structure. SiO 2 phenyl and SiO 2 300 have pores ranging from 9 to 14 nm in size, which also characterizes them as mesoporous substances. Al 2 O 3 and SiO 2 C2 have pore sizes of about 4 nm. Thus, the range of average pore diameter values of oxides studied in this work allows us to expect them to have similar sorption properties. However, the obtained data on the porous characteristics of the studied oxides elucidated the differences in their morphology, which will certainly influence the process of sorption of repellents on their surface. In particular, Al 2 O 3 and SiO 2 C2 have approximately the same porosity, but due to the differences in the sorbent structure they have different specific surface area, which can greatly influence the rate of sorption, as well as desorption, of substances on their surface. ZrO 2 is another prime example. It has the lowest specific surface area among other studied in this work sorbents, while its average pore size is about 46 nm, suggesting its possible high sorption activity towards repellents. However, the structural advantages of different compounds do not always correlate with the expected experimental data on the sorption of substances. Static sorption of DEET and IR3535 The results of static sorption of DEET and IR3535 on the surface of ZrO 2 , Al 2 O 3 , SiO 2 phenyl, SiO 2 C2 and SiO 2 300 showed that all studied oxides possess sorption properties (Fig. 3 ). The biggest decrease in the concentration of compounds being sorbed within 360 min occurred on SiO 2 phenyl. The lowest repellent sorption capacity, despite high surface area values calculated by the BET method, was seen in SiO 2 300. The obtained data suggest that both morphological parameters of the substances and their chemical nature are of particular importance in the sorption of DEET and IR3535. The adsorption isotherms obtained after the establishment of equilibrium also clearly show the differences in the sorption of DEET and IR3535 onto the studied oxides (Fig. 4 ). Thus, SiO 2 phenyl demonstrates high sorption capacity for both repellents. At the same time, zirconium and aluminum oxides showed high values of adsorption capacity Q max (251 mg/g and 231 mg/g, respectively) in relation to IR3535 (Fig. 5 ). Such a difference in sorption of DEET and IR3535 for these oxides can be explained by the chemical structure of repellent molecules, which directly affects the mass transfer processes of substances. Pointedly, it was found that despite having the largest pore volume and high specific surface area (compared to the other studied oxides), SiO 2 C2 has a significantly inferior sorption capacity in respect to other oxides, in particular SiO 2 phenyl, which can be explained by the presence of the phenyl group in the latter that has chemical affinity for repellent molecules. Obtained isotherms of SiO 2 300 also confirm the low sorption activity towards DEET, which can be explained by the structure of the repellent molecule. Thus, the sorption of DEET and IR3535 repellents does not directly depend on the morphology of the studied oxides. The study results showed that SiO 2 phenyl oxide has the highest sorption capacity for DEET (239 mg/g), while ZrO 2 , Al 2 O 3 , SiO 2 phenyl oxides – for IR3535 (251;231;221 mg/g, respectively), which makes these compounds suitable for their further use as repellent carrier substances. The most common isotherms (Langmuir, Freundlich, Temkin, Dubinin-Radushkevich, Hill-de Boer and Frumkin-Fowler-Guggenheim (FFG)) were chosen to describe in detail the static sorption of repellents on porous oxides and linear approximation parameters were calculated [ 29 ]. Results presented in Fig. 6 show that the sorption of DEET and IR3535 onto zirconium, aluminum and silicon oxides are better described by the Langmuir isotherm (Eq. 1 ), as indicated by the high values of the correlation coefficient (R 2 ) compared to the other isothermal models. The values of the separation factor R L (0 < R L <1), calculated by Eq. 2 , indicate a shift of adsorption equilibrium towards the sorption process. At the same time, the sorption of DEET onto the SiO 2 phenyl surface is best described by the Freundlich model (Eq. 3 ). Withal, the sorption of DEET onto the SiO 2 phenyl surface is best described by the Freundlich model (Eq. 3 ). Values of the coefficient n < 1 in this case indicate a chemical interaction between the sorbent and sorbate. For other sorption processes, values of the coefficient n ≥ 1 indicate that mainly the process physical sorption is happening. The Langmuir and Freundlich isotherm models are expressed by the following equations: Langmuir isotherm $$\frac{1}{{Q}_{e}}= \frac{1}{{Q}_{max}\bullet {K}_{L}}\frac{1}{{C}_{e}}+\frac{1}{{Q}_{max}}$$ 1 $${R}_{L}= \frac{1}{1+{K}_{L}{C}_{e}}$$ 2 Freundlich isotherm $$ln{Q}_{e}= ln{K}_{f}+\frac{1}{n}ln{C}_{e}$$ 3 where Q e is the quantity adsorbed by the unit mass of the adsorbent (mg/g), Q max is the capacity of the adsorbent monolayer (mg/g), C e is the adsorbate equilibrium concentration (mg/L), K L is the Langmuir adsorption constant, K f and n are Freundlich constants where the value of 1/n indicates the degree of linearity of isotherm. The isothermal Temkin model (Eq. 4 ) allows us to determine the energy of sorbate-sorbent interaction on the oxide surface. Temkin isotherm $${Q}_{e}= {B}_{T}ln{A}_{T}+{B}_{T}ln{C}_{e}$$ 4 where B T is the adsorption heat constant, and A T is the binding equilibrium constant. For all studied samples, the values of sorption heat B T of the repellents onto the considered sorbents were more than 8 kJ/mol, which may indirectly indicate the occurrence of chemosorption process. However, it is known that the Temkin model is valid only for certain linear sections and cannot be applied for the range of small and large values of concentrations, thus making it impossible to assess its applicability in full [ 30 ]. The occurrence of chemosorption process can be indirectly confirmed by the data calculated by the Dubinin-Radushkevich method, where the sorption energy of the sorbate E was more than 8 kJ/mol (Eq. 5 – 6 ). This method is used to determine the mechanism of sorption with Gaussian energy distribution in heterogeneous systems. Dubinin-Radushkevich isotherm $$lnQ=ln{Q}_{s}-\left(\beta {\epsilon }^{2}\right)$$ 5 $$E= \frac{1}{\surd 2\beta }$$ 6 where β is the Dubinin-Radushkevich isotherm constant; Qs is theoretically calculated adsorption capacity, mg/g; ε is the Polanyi potential (J/mol), E is the adsorption energy per one molecule of adsorbate, i.e., the energy needed to remove a molecule from the adsorbate’s surface (kJ/mol). Like Polanyi’s theory, the Dubinin-Radushkevich model is based on assumptions applicable for polymolecular sorption. At the same time, the obtained data suggests that primarily a monolayer formation of repellent molecules on porous oxides occurs. Moreover, relatively low values of the determination coefficient in this model (less than 0.95) for Al 2 O 3 , SiO 2 phenyl, SiO 2 C2 and SiO 2 300 do not allow to consider this model for the studied systems. The Frumkin-Fowler-Guggenheim (FFG) model is used to describe the sorption process of various pollutants from water (Eq. 7 ) [ 31 ]. Frumkin adsorption isotherm for aqueous systems relates the occupancy of sorption sites θ with the volume concentration Ce . Since this model is applicable to aqueous systems, we assumed it possible to apply it to elaborate our system, which comprised a solution of repellents in a polar solvent. This model allows us to calculate the binding energy of molecules to the solid sorbate [ 32 ]. Frumkin-Fowler-Guggenheim isotherm $${ln}\left(\frac{{C}_{e}\left(1-\theta \right)}{\theta }\right)-\frac{\theta }{1-\theta }=-ln{K}_{FG}+\frac{2W\theta }{RT}$$ 7 where K FG – isotherm constant, θ is a parameter used to describe the fraction of surface occupied by adsorbent molecules, W is the interaction energy between two adsorbed molecules on the adjacent neighboring site (kJ/mol), R is the gas constant (J/mol•K), Т is sorption temperature (K). The empirical sorption energy values were found to be negative W < 0 for all studied processes, indicating a repellent effect between the molecules of the sorbed repellents. Similarly to the Frumkin-Fowler-Guggenheim model, the Hil-de Boer model (Eq. 8 ) can be used to describe sorption in heterogeneous systems containing polar solvents [ 33 ]. The FFG model assumes a localized sorption process happening, while the Hil-de Boer model regards the formation of a mobile monolayer. Hil-de Boer isotherm $${ln}\left(\frac{{C}_{e}\left(1-\theta \right)}{\theta }\right)-\frac{\theta }{1-\theta }=-ln{K}_{1}-\frac{{K}_{2}\theta }{RT}$$ 8 where К 1 is the Hil-de Boer constant (L/mg), К 2 is the energetic constant of interaction between the adsorbed molecules (kJ/mol). The K 2 constant in the Hil-de Boer model describes the interaction energy of sorbate molecules on the sorbent surface. The values of constants for all studied sorption processes were negative, which also indicates repulsion of repellent molecules. Conclusions This work is dedicated to the study of the sorption properties of zirconia, alumina and silicas towards repellents; the morphological properties of these compounds were determined using SEM and BET methods. The obtained results showed that the synthesized zirconium and aluminum oxides, as well as silicon oxides, possess a well-developed mesoporous structure with various specific surface areas (34–380 g/m 2 ). The sorption capacity of zirconium, aluminum and silicon oxides to the most widely used repellents, DEET and IR3535, was also studied. SiO 2 phenyl and Al 2 O 3 showed the best sorption capacity towards the DEET repellent (239 and 119 mg/g, respectively), while ZrO 2 , Al 2 O 3 , SiO 2 phenyl showed a significant sorption capacity towards the IR3535 repellent (251; 231 and 221 mg/g, respectively). Such a difference in the sorption of these compounds can be explained by both the morphology of the sorbents and the amino groups present in the DEET and IR3535 molecules. Moreover, the obtained results showed that the large specific area of the sorbents is not a determining factor in the sorption of the repellents. Despite this, SiO 2 phenyl and Al 2 O 3 can be further utilized to create repellent materials based on DEET and IR3535. Isothermal models were used to calculate the parameters of repellent sorption onto ZrO 2 , Al 2 O 3 , SiO 2 phenyl, SiO 2 C2 and SiO 2 300. It showed that this process is best described by the Langmuir model, which confirms that the maximum adsorption capacity is reached when a sorbent monolayer is formed. Declarations Acknowledgements The authors are grateful to the staff of the Nanyang Technological University (Singapore) and the staff of the Center for Instrumental Chemical Analysis and Complex Investigation of Substances and Materials of RTU MIREA (Russia) for their assistance in conducting physicochemical studies. Funding The work was carried out at the expense of the industry research program of Rospotrebnadzor for 2024-2025 (No. 1023032900395-5-1.6.23) and supported by Singapore MAR grant 04INS000458C150OOE01. Author contributions Sergei. A. Zverev: Investigation, Original draft. Yana. V. Vinogradova: Investigation. Anna. A. Selivanova: Investigation. Roman. D. Solovov: Methodology, Resources. Konstantin. A. Sakharov: Visualization, Review & Editing. Anatoliy. A. Ischenko: Supervision. Sergei. V. Andreev: Original draft, Project administration. Authors declare not to have any conflicts of interest. Ethical Approval Not applicable Availability of data and materials The manuscript reports the complete dataset. If needed, the corresponding author can be contacted via email for further calculations. References Annandarajah C. et al. Biobased plastics with insect‐repellent functionality //Polymer Engineering & Science. 2019. V. 59. №. s2. P. E460-E467. https://doi.org/10.1002/pen.25083 da Silva M. R. M., Ricci-Júnior E . An approach to natural insect repellent formulations: from basic research to technological development //Acta tropica. 2020. V. 212. P. 105419. https://doi.org/10.1016/j.actatropica.2020.105419 Nogueira Barradas T. et al. Polymer-based drug delivery systems applied to insects repellents devices: a review //Current drug delivery. 2016. V. 13. №. 2. P. 221-235. World Health Organization. World malaria report 2022. – World Health Organization, 2022. Climate change and health [Electronic resource]. URL: https://www.who.int/news-room/fact-sheets/detail/climate-change-and-health. Emam H. E., Abdelhameed R. M. In-situ modification of natural fabrics by Cu-BTC MOF for effective release of insect repellent (N, N-diethyl-3-methylbenzamide) //Journal of Porous Materials. 2017. V. 24. P. 1175-1185. https://doi.org/10.1007/s10934-016-0357-y Tavares M. et al . Trends in insect repellent formulations: A review //International journal of pharmaceutics. 2018. V. 539. №. 1-2. P. 190-209. https://doi.org/10.1016/j.ijpharm.2018.01.046 Du F. et al. 3D-Printing of the polymer/insect-repellent system poly (L-lactic acid)/ethyl butylacetylaminopropionate (PLLA/IR3535) //International Journal of Pharmaceutics. 2022. V. 624. P. 122023. https://doi.org/10.1016/j.ijpharm.2022.122023 Xiang C. et al. Structure and properties of polyamide fabrics with insect-repellent functionality by electrospinning and oxygen plasma-treated surface coating //Polymers. 2020. V. 12. №. 10. P. 2196. https://doi.org/10.3390/polym12102196 Richoux G. M. et al. Structure–activity relationship analysis of potential new vapor-active insect repellents //Journal of Agricultural and Food Chemistry. 2020. V. 68. №. 47. P. 13960-13969. https://doi.org/10.1021/acs.jafc.0c03333 Paul R. (ed.). Functional finishes for textiles: improving comfort, performance and protection. Elsevier, 2014. Elsayed G. A., Hassabo A. G. Insect repellent of cellulosic fabrics (a review) //Letters in Applied NanoBioScience. 2022. V. 11. №. 1. P. 3181-3190. https://doi.org/10.33263/LIANBS111.31813190 Song J. Y., Bhadra B. N., Jhung S. H. Contribution of H-bond in adsorptive removal of pharmaceutical and personal care products from water using oxidized activated carbon //Microporous and Mesoporous Materials. 2017. V. 243. P. 221-228. https://doi.org/10.1016/j.micromeso.2017.02.024 Trouvé A. et al. Tuning the hydrophobicity of mesoporous silica materials for the adsorption of organic pollutant in aqueous solution //Journal of hazardous materials. 2012. V. 201. P. 107-114. https://doi.org/10.1016/j.jhazmat.2011.11.043 Marocco A. et al. Removal of Agrochemicals from Waters by Adsorption: A Critical Comparison among Humic-Like Substances, Zeolites, Porous Oxides, and Magnetic Nanocomposites //Processes. 2020. V. 8. №. 2. P. 141. https://doi.org/10.3390/pr8020141 Blachnio M. et al. Adsorption of Phenoxyacetic Herbicides from Water on Carbonaceous and Non-Carbonaceous Adsorbents //Molecules. 2023. V. 28. №. 14. P. 5404. https://doi.org/10.3390/molecules28145404 Wang L. et al. Rational design, synthesis, adsorption principles and applications of metal oxide adsorbents: a review //Nanoscale. 2020. V. 12. №. 8. P. 4790-4815. https://doi.org/10.1039/C9NR09274A Ravindhranath K., Ramamoorty M. Nano aluminum oxides as adsorbents in waterremediation methods: a review //Rasayan J. Chem. 2017. V. 10. P. 716-722. http://dx.doi.org/10.7324/RJC.2017.1031762 Zotov R. et al. Influence of the composition, structure, and physical and chemical properties of aluminium-oxide-based sorbents on water adsorption ability //Materials. 2018. V. 11. №. 1. P. 132. https://doi.org/10.3390/ma11010132 Reshetnikov S. et al. Effect of particle size on adsorption kinetics of water vapor on porous aluminium oxide material //Journal of Physics: Conference Series. IOP Publishing, 2019. V. 1145. №. 1. P. 012033. https://doi.org/10.1088/1742-6596/1145/1/012033 Youssef W. M., Hagag M. S., Ali A. H . Synthesis, characterization and application of composite derived from rice husk ash with aluminium oxide for sorption of uranium //Adsorption Science & Technology. 2018. V. 36. №. 5-6. P. 1274-1293. https://doi.org/10.1177/0263617418768920 Hussain T. et al. Biogenic synthesis of date stones biochar-based zirconium oxide nanocomposite for the removal of hexavalent chromium from aqueous solution //Applied Nanoscience. 2022. P. 1-14. https://doi.org/10.1007/s13204-022-02599-z Dubey S. S., Grandhi S. Sorption studies of yttrium (III) ions on surfaces of nano-thorium (IV) oxide and nano-zirconium (IV) oxide //International Journal of Environmental Science and Technology. 2019. V. 16. P. 59-70. https://doi.org/10.1007/s13762-017-1589-3 Abass M. R., El-Kenany W. M., Eid M. A. Sorption of cesium and gadolinium ions onto zirconium silico antimonate sorbent from aqueous solutions //Applied Radiation and Isotopes. 2023. V. 192. P. 110542. https://doi.org/10.1016/j.apradiso.2022.110542 Rahman N., Varshney P., Nasir M . Synthesis and characterization of polydopamine/hydrous zirconium oxide composite and its efficiency for the removal of uranium (VI) from water //Environmental Nanotechnology, Monitoring & Management. 2021. V. 15. P. 100458. https://doi.org/10.1016/j.enmm.2021.100458 Shen D. et al. Fabricating ultrafine zirconium oxide based composite sorbents in “soft confined space” for efficiently removing fluoride from environmental water //Chemical Engineering Journal. 2022. V. 444. P. 136199. https://doi.org/10.1016/j.cej.2022.136199 Rezaee S., Ranjbar K., Kiasat A. R. The effect of surfactant on the sol–gel synthesis of alumina-zirconia nanopowders //Ceramics International. 2018. V. 44. №. 16. P. 19963-19969. https://doi.org/10.1016/j.ceramint.2018.07.263 Bardestani R., Patience G. S., Kaliaguine S. Experimental methods in chemical engineering: specific surface area and pore size distribution measurements—BET, BJH, and DFT //The Canadian Journal of Chemical Engineering. 2019. V. 97. №. 11. P. 2781-2791. https://doi.org/10.1002/cjce.23632 Ragadhita R., Nandiyanto A. B. D. How to calculate adsorption isotherms of particles using two-parameter monolayer adsorption models and equations //Indonesian Journal of Science and Technology. 2021. V. 6. №. 1. P. 205-234. https://doi.org/10.17509/ijost.v6i1.32354 Chu K. H. Revisiting the Temkin isotherm: Dimensional inconsistency and approximate forms //Industrial & Engineering Chemistry Research. 2021. V. 60. №. 35. P. 13140-13147. https://doi.org/10.1021/acs.iecr.1c01788 Chu K. H., Tan B. C. Is the Frumkin (Fowler–Guggenheim) adsorption isotherm a two-or three-parameter equation? //Colloid and Interface Science Communications. 2021. V. 45. – P. 100519. https://doi.org/10.1016/j.colcom.2021.100519 Tovbin Y. K. The Molecular Theory of Adsorption in Porous Solids. // CRC Press. 2017 Chu K. H. et al. S-shaped adsorption isotherms modeled by the Frumkin–Fowler–Guggenheim and Hill–de Boer equations //Monatshefte für Chemie-Chemical Monthly. 2023. P. 1-9. https://doi.org/10.1007/s00706-023-03116-w. Additional Declarations No competing interests reported. Supplementary Files Graphicalabstarct.jpg Cite Share Download PDF Status: Published Journal Publication published 16 May, 2024 Read the published version in Colloid and Polymer Science → Version 1 posted Editorial decision: Revision requested 03 Apr, 2024 Reviews received at journal 01 Apr, 2024 Reviewers agreed at journal 22 Mar, 2024 Reviewers invited by journal 22 Mar, 2024 Submission checks completed at journal 23 Feb, 2024 Editor assigned by journal 23 Feb, 2024 First submitted to journal 20 Feb, 2024 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. We do this by developing innovative software and high quality services for the global research community. Our growing team is made up of researchers and industry professionals working together to solve the most critical problems facing scientific publishing. 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-3972861","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":274428195,"identity":"1b56311b-052e-4dc3-970d-97607bf613ec","order_by":0,"name":"Sergei A. Zverev","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAABBElEQVRIiWNgGAWjYHADHiA2kJADMQ88IF5LhYUxWEsC8VrOVCQ2gNj4tMjPSD724WMbgz0D+9mDj262SaTPDzv8EGiLnZxuA3YtjDPSkmfObGNIbODJSzbObZPI3Xg7zQCoJdnY7AB2Lcw8Z4yBGOgSCR4zabCW2QkgLQcSt+HQwsZz/jPznzNAh0nwmP8Gakk3nJ3+Aa8WHvYeZmaGCgbGBqAtzDlnJBLkpXPw2yLB3mbM2FMhkdjGk2MsnVMhYbhBOqfgQIIBbr/INzM/ZvhhYGPPz37G8HOOQZ28/Oz0zR8+VNjJ4dICs4yBDcY0AKs0wKsc3d4GUlSPglEwCkbBSAAAp5lVOap8YBIAAAAASUVORK5CYII=","orcid":"","institution":"Disinfectology Institute of F.F. Erisman FSCH of Rospotrebnadzor","correspondingAuthor":true,"prefix":"","firstName":"Sergei","middleName":"A.","lastName":"Zverev","suffix":""},{"id":274428196,"identity":"0048b2a7-16ff-436d-bb96-848eeaec3475","order_by":1,"name":"Yana V. Vinogradova","email":"","orcid":"","institution":"MIREA – Russian Technological University (M.V. Lomonosov Institute of Fine Chemical Technologies)","correspondingAuthor":false,"prefix":"","firstName":"Yana","middleName":"V.","lastName":"Vinogradova","suffix":""},{"id":274428197,"identity":"471f827e-8070-4bdd-bbf4-ccb56ef3a62c","order_by":2,"name":"Anna A. Selivanova","email":"","orcid":"","institution":"MIREA – Russian Technological University (M.V. Lomonosov Institute of Fine Chemical Technologies)","correspondingAuthor":false,"prefix":"","firstName":"Anna","middleName":"A.","lastName":"Selivanova","suffix":""},{"id":274428198,"identity":"2ffc7beb-1d78-4ff9-bb02-e0e3fda52da0","order_by":3,"name":"Roman D. Solovov","email":"","orcid":"","institution":"Russian Academy of Science","correspondingAuthor":false,"prefix":"","firstName":"Roman","middleName":"D.","lastName":"Solovov","suffix":""},{"id":274428199,"identity":"ebd5b1c5-cee5-4c2f-8db2-2c4b516afedb","order_by":4,"name":"Konstantin A. Sakharov","email":"","orcid":"","institution":"Nanyang Technological University","correspondingAuthor":false,"prefix":"","firstName":"Konstantin","middleName":"A.","lastName":"Sakharov","suffix":""},{"id":274428200,"identity":"8166ab00-6e14-4de9-8a67-b9f990017c76","order_by":5,"name":"Anatoliy A. Ischenko","email":"","orcid":"","institution":"MIREA – Russian Technological University (M.V. Lomonosov Institute of Fine Chemical Technologies)","correspondingAuthor":false,"prefix":"","firstName":"Anatoliy","middleName":"A.","lastName":"Ischenko","suffix":""},{"id":274428201,"identity":"4c364d23-e0c8-4bad-98a5-02bf270558b3","order_by":6,"name":"Sergei V. Andreev","email":"","orcid":"","institution":"Disinfectology Institute of F.F. Erisman FSCH of Rospotrebnadzor","correspondingAuthor":false,"prefix":"","firstName":"Sergei","middleName":"V.","lastName":"Andreev","suffix":""}],"badges":[],"createdAt":"2024-02-20 13:17:51","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-3972861/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-3972861/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1007/s00396-024-05260-z","type":"published","date":"2024-05-16T08:02:47+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":51716579,"identity":"65667737-952a-4c00-8be6-e79219017457","added_by":"auto","created_at":"2024-02-27 21:09:46","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":445900,"visible":true,"origin":"","legend":"\u003cp\u003eScanning electron microscopy images of ZrO\u003csub\u003e2 \u003c/sub\u003e(A), Al\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e (B), SiO\u003csub\u003e2\u003c/sub\u003e phenyl (C), SiO\u003csub\u003e2 \u003c/sub\u003eC2 (D) and SiO\u003csub\u003e2\u003c/sub\u003e 300 (E) oxides at 1-2 μm resolution\u003cstrong\u003e.\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"fig1.png","url":"https://assets-eu.researchsquare.com/files/rs-3972861/v1/58c61fe0d0e9db0476b381ac.png"},{"id":51716580,"identity":"04ada343-cc6a-4ac6-bc9f-ed3fe7619fb2","added_by":"auto","created_at":"2024-02-27 21:09:46","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":204802,"visible":true,"origin":"","legend":"\u003cp\u003eLow-temperature nitrogen adsorption-desorption isotherms (77 K) of ZrO\u003csub\u003e2\u003c/sub\u003e (A), Al\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e (B), SiO\u003csub\u003e2\u003c/sub\u003e phenyl (C), SiO\u003csub\u003e2\u003c/sub\u003e C2 (D), and SiO\u003csub\u003e2\u003c/sub\u003e 300 (E) oxides.\u003c/p\u003e","description":"","filename":"fig2.png","url":"https://assets-eu.researchsquare.com/files/rs-3972861/v1/5621c13fd3b89d40465b08ce.png"},{"id":51716582,"identity":"d5e80858-1722-44b5-9ef3-a71a34bd0a7d","added_by":"auto","created_at":"2024-02-27 21:09:46","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":140673,"visible":true,"origin":"","legend":"\u003cp\u003eChanges in DEET (I) and IR3535 (II) concentration as a result of repellent sorption on ZrO\u003csub\u003e2\u003c/sub\u003e, Al\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e, SiO\u003csub\u003e2\u003c/sub\u003e phenyl, SiO\u003csub\u003e2 \u003c/sub\u003eC2, and SiO\u003csub\u003e2\u003c/sub\u003e 300.\u003c/p\u003e","description":"","filename":"fig3.png","url":"https://assets-eu.researchsquare.com/files/rs-3972861/v1/8421ba7bb14ed4af91d50c5f.png"},{"id":51716584,"identity":"90ed5b21-7c75-4fe4-955e-b6c4fc5abc74","added_by":"auto","created_at":"2024-02-27 21:09:46","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":151437,"visible":true,"origin":"","legend":"\u003cp\u003eNonlinear adsorption isotherms of DEET (I) and IR3535 (II) on ZrO\u003csub\u003e2\u003c/sub\u003e, Al\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e, SiO\u003csub\u003e2\u003c/sub\u003e phenyl, SiO\u003csub\u003e2\u003c/sub\u003e C2, and SiO\u003csub\u003e2\u003c/sub\u003e 300 oxides\u003cstrong\u003e.\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"fig4.png","url":"https://assets-eu.researchsquare.com/files/rs-3972861/v1/5032226c316bcb501fae9098.png"},{"id":51716585,"identity":"81583711-ef3c-433e-adbc-6acf276978af","added_by":"auto","created_at":"2024-02-27 21:09:46","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":92264,"visible":true,"origin":"","legend":"\u003cp\u003eDiagrams of adsorption capacity changes of ZrO\u003csub\u003e2\u003c/sub\u003e, Al\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e, SiO\u003csub\u003e2\u003c/sub\u003e phenyl, SiO\u003csub\u003e2\u003c/sub\u003e C2, and SiO\u003csub\u003e2\u003c/sub\u003e 300 oxides for DEET (A) and IR3535 (B) repellents.\u003c/p\u003e","description":"","filename":"fig5.png","url":"https://assets-eu.researchsquare.com/files/rs-3972861/v1/c4462eef13f38d895809d374.png"},{"id":51716583,"identity":"255e392d-e79e-49de-9ba0-1118b35e0956","added_by":"auto","created_at":"2024-02-27 21:09:46","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":308962,"visible":true,"origin":"","legend":"\u003cp\u003eComparison of the theoretical models used to describe the sorption of DEET (black line) and IR3535 (gray line) onto ZrO\u003csub\u003e2\u003c/sub\u003e (A), Al\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e (B), SiO\u003csub\u003e2\u003c/sub\u003e phenyl (C), SiO\u003csub\u003e2 \u003c/sub\u003eC2 (D), and SiO\u003csub\u003e2\u003c/sub\u003e 300 (E) oxides\u003cstrong\u003e.\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"6.png","url":"https://assets-eu.researchsquare.com/files/rs-3972861/v1/7f977dacb0c7d7725bf23b78.png"},{"id":60795976,"identity":"b2e6a7dc-411c-4334-88b4-65f41d9a6279","added_by":"auto","created_at":"2024-07-22 08:02:53","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":1894983,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-3972861/v1/52ccbe3e-3301-4ca9-adbc-8a6244a954b4.pdf"},{"id":51717738,"identity":"57bd7497-565e-424d-b064-c7a6512d722b","added_by":"auto","created_at":"2024-02-27 21:17:46","extension":"jpg","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":121073,"visible":true,"origin":"","legend":"","description":"","filename":"Graphicalabstarct.jpg","url":"https://assets-eu.researchsquare.com/files/rs-3972861/v1/724fbedfe63a63a77dde8e83.jpg"}],"financialInterests":"No competing interests reported.","formattedTitle":"Study of sorption properties of zirconia, alumina and silica in relation to repellents","fulltext":[{"header":"Introduction","content":"\u003cp\u003eClimate changes in the past decades have led to a significant increase in the number of various diseases caused by bloodsucking arthropods [\u003cspan additionalcitationids=\"CR2 CR3\" citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e]. According to the World Health Organization (WHO), due to the climate changes in 2030\u0026ndash;2050, the malaria mortality rate may increase to 250 000 cases. [\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]. In particular, this can be explained by the fact that the mosquitoes are able to quickly adapt to the environmental changes, which leads to their fast reproduction and migration in the settings of higher temperatures and wet climate [\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eBloodsucking arthropods are the cause of disease in more than 700\u0026nbsp;million people yearly, with every 17th case leading to death [\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e]. To protect people and prevent the spreading of virulent diseases, products and materials with repellent properties are widely used. \u003cem\u003eN,N\u003c/em\u003e-diethyl-3-methylbenzamide (DEET), \u003cem\u003eN,N\u003c/em\u003e-diethylphenylacetamide (DEEPA), ethyl 3-[acetyl(butyl)amino]propionate (IR3535) and icaridin (KBR 3023) are considered the classical synthetic repellents [\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e, \u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e]. These compounds are able to effectively repel mosquitoes and some other bloodsucking arthropods. However, their use typically implies applying the compounds directly onto the skin, which may cause irritation and allergy. Moreover, it is known that DEET is able to diffuse through the layers of skin and reach the bloodstream [\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e]. On the other hand, natural repellants based on citronella, geranium, lantana, etc. essential oils are widely used as well. Agents based on them have low toxicity, thus less prominent side effects; however, they are noted to have lower repellent activity [\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eSearching for new compounds and novel approaches to ensure the epidemiological welfare of the population is becoming the growing tendency among modern research [\u003cspan additionalcitationids=\"CR2\" citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e, \u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e, \u003cspan additionalcitationids=\"CR9\" citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e]. One of those directions is developing materials for manufacturing special protective clothing with insecticide and repellent properties [\u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e]. E.g., sol-gel technology allows obtaining textile, coated with silica nanoparticles impregnated with permethrin [\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e]. Such coating allows ensuring a high level of protection from insect bites without losing its physical properties. Moreover, textile obtained through sol-gel technique are stable in regards to environmental exposure, which is confirmed by the intact efficacy of the insecticide-impregnated textile after washing.\u003c/p\u003e \u003cp\u003eTo endow the materials with required properties, a method of sorption of active substances on the surface of sorbents is also used. For example, pesticides, repellents and herbicides sorption on organic sorbents have been studied extensively in modern literature, however, most of the studies are dedicated to the problem of wastewater and soil treatment for pollutants removal [\u003cspan additionalcitationids=\"CR14 CR15\" citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e]. Study results show that inorganic compounds, such as activated charcoal and other allotropic modification of carbon, silicon oxides and metal oxides are able to selectively sorb on their surface, required compounds with high efficiency. However, these properties of the inorganic compounds are suitable for implementation not only in wastewater treatment system but also in other areas, namely designing of material with specific properties.\u003c/p\u003e \u003cp\u003eIt is known that synthesized ZrO\u003csub\u003e2\u003c/sub\u003e and Al\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e possess high sorption properties [\u003cspan additionalcitationids=\"CR18 CR19 CR20 CR21 CR22 CR23 CR24 CR25\" citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e]. Their unique properties, such as large surface area, large pore volume, high porosity, high physical and chemical stability, make them stand out among other sorbents [\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e]. Due to a presence of acid and basic centers on their surface, aluminium and zirconium oxides have affinity for representatives of various substances classes, e.g., compounds of uranium, chromium(VI), yttrium(III), etc., which allows selective sorption of compounds of these metals from different objects [\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e, \u003cspan additionalcitationids=\"CR22 CR23 CR24\" citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e]. An important feature of this kind of research is the study of kinetic and isothermal parameters as they make it possible to describe the characteristics of the mass transfer process of substances. Calculated characteristics allow us not only to analyze the data on sorption diffuse parameters but also to increase the adsorption capacity of developed materials.\u003c/p\u003e \u003cp\u003eIn this work, the sorption capacity of aluminium, zirconium and silicon oxides with functional groups for DEET and IR3535 repellents was studied; thermodynamic parameters of sorption were calculated and potential application of the obtained composite compounds as an active component of materials with repellent properties was evaluated.\u003c/p\u003e"},{"header":"Experimental","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003eMaterials\u003c/h2\u003e \u003cp\u003e \u003cem\u003eN,N\u003c/em\u003e-diethyl-3-methylbenzamide (DEET) was purchased from Sigma Aldrich (USA); ethyl 3-[acetyl(butyl)amino] propionate (IR3535) was purchased from Merck KGaA (Darmstadt, Germany); acetonitrile was purchased from Honeywell (Charlotte, North Carolina, USA); aluminum nitrate nonahydrate, zirconyl nitrate dihydrate, ammonium nitrate, citric acid hydrate and ethylene glycol used were from JSC LenReactiv (St. Petersburg, Russia); Silasorb С2 (SiO\u003csub\u003e2\u003c/sub\u003e C2), Silasorb phenyl (SiO\u003csub\u003e2\u003c/sub\u003e phenyl), Silasorb 300 (SiO\u003csub\u003e2\u003c/sub\u003e 300) used were from Elsico (Moscow, Russia).\u003c/p\u003e \u003cp\u003eAll other reagents were analytical grade or higher and used without further purification.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec4\" class=\"Section2\"\u003e \u003ch2\u003eMethods\u003c/h2\u003e \u003cdiv id=\"Sec5\" class=\"Section3\"\u003e \u003ch2\u003eSynthesis of ZrO\u003csub\u003e2\u003c/sub\u003e and Al\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e\u003c/h2\u003e \u003cp\u003eZrO\u003csub\u003e2\u003c/sub\u003e synthesis was carried out according to the following technique. 49 g of 0.97 mol/L zirconyl nitrate solution was dissolved in deionized water in a 1000 cm\u003csup\u003e3\u003c/sup\u003e glass beaker, then 197 g of ammonium nitrate was added. The beaker was placed on a hotplate with controlled heating, and the solution was gradually heated to 80\u0026deg;C for two hours while constantly stirred. Thirty minutes after the dissolution of the salts, 38 g of citric acid was added. After reaching 80\u0026deg;C, the temperature of the solution was gradually increased at a rate of 5\u0026ndash;7\u0026deg;C/h. Two hours after the dissolution of citric acid, 11 g of ethylene glycol was added, and the temperature was increased to 95\u0026deg;C. When the solution was evaporated to a viscous paste, it was transferred to an evaporation bowl and placed in a steel enameled container and exposed to further heating up to 800 ℃. During the synthesis, a blackish-gray powder with a distinctive coral-shaped structure was formed. The obtained product containing zirconium oxide was calcined in the air at 800\u0026deg;C for no less than 2 hours.\u003c/p\u003e \u003cp\u003eThe synthesis and heat treatment of aluminium oxide was carried out in the similar fashion. To achieve the desired results, 7 g of aluminium nitrate, 230 g of ammonium nitrate, 45 g of citric acid and 13 g of ethylene glycol were used. The average yield for both products was found to be around 96%.\u003c/p\u003e \u003c/div\u003e \u003c/div\u003e \u003cdiv id=\"Sec6\" class=\"Section2\"\u003e \u003ch2\u003eScanning Electron Microscopy (SEM)\u003c/h2\u003e \u003cp\u003eMorphology of the oxide samples was studied on SUPRA 55 Field Emission Scanning Electron Microscope (Carl Zeiss, Oberkochen, Germany) using an SE2 detector under 1kV accelerating voltage.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec7\" class=\"Section2\"\u003e \u003ch2\u003eAnalysis of specific surface area of the oxides according to the Brunauer\u0026ndash;Emmett\u0026ndash;Teller theory\u003c/h2\u003e \u003cp\u003eThe specific surface area and pore volume of the oxide samples were calculated using the Brunauer\u0026ndash;Emmett\u0026ndash;Teller method, with the experiments being performed on a Beckman Coulter SA 3100 analyzer (Indianapolis, US).\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec8\" class=\"Section2\"\u003e \u003ch2\u003eStatic sorption of DEET and IR3535\u003c/h2\u003e \u003cp\u003eDEET and IR3535 isothermal sorption process was carried out by mixing 100 mg of zirconia, alumina or silica with repellent solutions (C\u003csub\u003esolutions\u003c/sub\u003e = 100\u0026ndash;1000 mg/L) in 40 ml of acetonitrile for 120 min at 24\u0026thinsp;\u0026plusmn;\u0026thinsp;1\u0026deg;C. To determine changes in the concentration of repellent solutions, samples were collected after 5, 15, 30, 60, 120, and 360 min and filtered through 0.45 \u0026micro;m PTFE filter. The optical density of DEET and IR3535 in the analyzed samples was recorded on a Varian Cary 50 UV-Vis spectrophotometer (Utah, USA) in the spectral range of 190\u0026ndash;210 nm. Concentrations of DEET and IR3535 in the samples were calculated using absolute calibration method.\u003c/p\u003e \u003cp\u003eThe DEET and IR3535 repellent solutions that were used to plot the calibration curves were prepared by dilution the stock solution. Stock solution was prepared by accurately measuring the necessary amount of the compound to an approximation of the fourth decimal number, and diluting it in acetonitrile.\u003c/p\u003e \u003c/div\u003e"},{"header":"Results and discussion","content":"\u003cp\u003eAlumina, zirconia and silica were chosen as potential repellent carrier substances as inorganic compounds with high sorption capacity as a result of searching for new way to produce repellent materials. To obtain compounds with high porous surface area, ZrO\u003csub\u003e2\u003c/sub\u003e and Al\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e were synthesized using the glycol-citrate method. This method allows obtaining porous metal oxides with desired structural characteristics and low content of by-products [\u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eSiO\u003csub\u003e2\u003c/sub\u003e phenyl, SiO\u003csub\u003e2\u003c/sub\u003e C2, SiO\u003csub\u003e2\u003c/sub\u003e 300 were commercially purchased and used without purification. Choosing silica is explained by their various properties provided due to the presence of functional groups: SiO\u003csub\u003e2\u003c/sub\u003e 300 contains no functional groups and is hydrophilic; SiO\u003csub\u003e2\u003c/sub\u003e C2 contains alkyl radicals; SiO\u003csub\u003e2\u003c/sub\u003e phenyl contains phenyl groups that may provide additional affinity for DEET and IR3535 through interaction of the π-system with the amino groups of the repellents.\u003c/p\u003e \u003cp\u003eSEM and BET methods were used to study the morphology and sorption characteristics of the obtained oxides. Data analysis showed that the combination of these methods allows us to evaluate the possibility of using these oxides as carrier sorbents.\u003c/p\u003e \u003cdiv id=\"Sec10\" class=\"Section2\"\u003e \u003ch2\u003eScanning Electron Microscopy (SEM)\u003c/h2\u003e \u003cp\u003eSEM results analysis shows that zirconium (A) and aluminum (B) oxides posses a distinct lamellar structure with a thickness of 40\u0026ndash;50 nm, which is an inherent trait of substances obtained by the glycol-citrate synthesis method (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e). The inner porous structure is also clearly visible, which can imply the existence of potential sorption centers. SiO\u003csub\u003e2\u003c/sub\u003e phenyl (C) and SiO\u003csub\u003e2\u003c/sub\u003e C2 (D) possess asymmetrical cubic shape with different structural irregularities. SiO\u003csub\u003e2\u003c/sub\u003e 300 (E) has a structure consisting of densely packed spherical objects with an average diameter of 10 \u0026micro;m. Silica, like zirconia and alumina, has a prominent porous structure, which allows assuming their high sorption properties.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec11\" class=\"Section2\"\u003e \u003ch2\u003eBrunauer\u0026ndash;Emmett\u0026ndash;Teller (BET) theory\u003c/h2\u003e \u003cp\u003eBET method, consisting of the low-temperature nitrogen adsorption-desorption process on the surface of the studied samples, was used to calculate the specific surface area of porous zirconium, aluminum, and silicon oxides (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e). The Barrett-Joyner-Halenda (BJH) method was used to calculate the pore size distribution and determine the average pore size [\u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e]. The parameters of the porous structure of the samples are presented in Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\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\u003ePorosity parameters of zirconium, aluminum, SiO\u003csub\u003e2\u003c/sub\u003e phenyl, SiO\u003csub\u003e2\u003c/sub\u003e C2, and SiO\u003csub\u003e2\u003c/sub\u003e 300 oxides calculated using the BJH method.\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"5\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\"\u0026plusmn;\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\"\u0026plusmn;\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\"\u0026plusmn;\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\"\u0026plusmn;\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eSorbent\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eSpecific surface area, m\u003csup\u003e2\u003c/sup\u003e/g\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eMonolayer volume, cc/g\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eAverage pore volume, cc/g\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eAverage pore size, nm\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eZrO\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\"\u0026plusmn;\" colname=\"c2\"\u003e \u003cp\u003e34.3\u0026thinsp;\u0026plusmn;\u0026thinsp;1.7\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\"\u0026plusmn;\" colname=\"c3\"\u003e \u003cp\u003e7.88\u0026thinsp;\u0026plusmn;\u0026thinsp;0.39\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\"\u0026plusmn;\" colname=\"c4\"\u003e \u003cp\u003e0.0865\u0026thinsp;\u0026plusmn;\u0026thinsp;0.0043\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\"\u0026plusmn;\" colname=\"c5\"\u003e \u003cp\u003e46.0\u0026thinsp;\u0026plusmn;\u0026thinsp;2.3\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eAl\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\"\u0026plusmn;\" colname=\"c2\"\u003e \u003cp\u003e85.5\u0026thinsp;\u0026plusmn;\u0026thinsp;4.3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\"\u0026plusmn;\" colname=\"c3\"\u003e \u003cp\u003e19.6\u0026thinsp;\u0026plusmn;\u0026thinsp;1.0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\"\u0026plusmn;\" colname=\"c4\"\u003e \u003cp\u003e0.119\u0026thinsp;\u0026plusmn;\u0026thinsp;0.006\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\"\u0026plusmn;\" colname=\"c5\"\u003e \u003cp\u003e3.84\u0026thinsp;\u0026plusmn;\u0026thinsp;0.19\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eSiO\u003csub\u003e2\u003c/sub\u003e phenyl\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\"\u0026plusmn;\" colname=\"c2\"\u003e \u003cp\u003e211\u0026thinsp;\u0026plusmn;\u0026thinsp;11\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\"\u0026plusmn;\" colname=\"c3\"\u003e \u003cp\u003e48.4\u0026thinsp;\u0026plusmn;\u0026thinsp;2.4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\"\u0026plusmn;\" colname=\"c4\"\u003e \u003cp\u003e0.161\u0026thinsp;\u0026plusmn;\u0026thinsp;0.008\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\"\u0026plusmn;\" colname=\"c5\"\u003e \u003cp\u003e9.85\u0026thinsp;\u0026plusmn;\u0026thinsp;0.49\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eSiO\u003csub\u003e2\u003c/sub\u003e C2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\"\u0026plusmn;\" colname=\"c2\"\u003e \u003cp\u003e380\u0026thinsp;\u0026plusmn;\u0026thinsp;19\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\"\u0026plusmn;\" colname=\"c3\"\u003e \u003cp\u003e87.3\u0026thinsp;\u0026plusmn;\u0026thinsp;4.4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\"\u0026plusmn;\" colname=\"c4\"\u003e \u003cp\u003e0.306\u0026thinsp;\u0026plusmn;\u0026thinsp;0.015\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\"\u0026plusmn;\" colname=\"c5\"\u003e \u003cp\u003e3.84\u0026thinsp;\u0026plusmn;\u0026thinsp;0.19\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eSiO\u003csub\u003e2\u003c/sub\u003e 300\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\"\u0026plusmn;\" colname=\"c2\"\u003e \u003cp\u003e273\u0026thinsp;\u0026plusmn;\u0026thinsp;14\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\"\u0026plusmn;\" colname=\"c3\"\u003e \u003cp\u003e62.7\u0026thinsp;\u0026plusmn;\u0026thinsp;3.1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\"\u0026plusmn;\" colname=\"c4\"\u003e \u003cp\u003e0.304\u0026thinsp;\u0026plusmn;\u0026thinsp;0.015\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\"\u0026plusmn;\" colname=\"c5\"\u003e \u003cp\u003e13.8\u0026thinsp;\u0026plusmn;\u0026thinsp;0.7\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\u003eThe presented BET isotherms show that when the value of relative pressure P\u003csub\u003es\u003c/sub\u003e/P\u003csub\u003e0\u003c/sub\u003e is less than 1, the nitrogen adsorption capacity increases rapidly for all oxides, which indicates the mesoporous structure of the studied compounds (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e). When the value of relative pressure P\u003csub\u003es\u003c/sub\u003e/P\u003csub\u003e0\u003c/sub\u003e is more than 0.4, a hysteresis loop is observed for all curves, indicating the formation of capillary condensation for all oxides.\u003c/p\u003e \u003cp\u003eData analysis of the specific surface area and pore sizes calculations of the studied oxides showed that silicon oxides SiO\u003csub\u003e2\u003c/sub\u003e C2, SiO\u003csub\u003e2\u003c/sub\u003e 300 and SiO\u003csub\u003e2\u003c/sub\u003e phenyl (211\u0026thinsp;\u0026divide;\u0026thinsp;380 m\u003csup\u003e2\u003c/sup\u003e/g) have a larger area compared to synthetic zirconium and aluminum oxides (34.3 and 85.5 m\u003csup\u003e2\u003c/sup\u003e/g, respectively). The obtained data also shows a significant difference in pore size for each of the oxides. ZrO\u003csub\u003e2\u003c/sub\u003e has pores of around 46.0 nm in size, indicating its mesoporous structure. SiO\u003csub\u003e2\u003c/sub\u003e phenyl and SiO\u003csub\u003e2\u003c/sub\u003e 300 have pores ranging from 9 to 14 nm in size, which also characterizes them as mesoporous substances. Al\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e and SiO\u003csub\u003e2\u003c/sub\u003e C2 have pore sizes of about 4 nm. Thus, the range of average pore diameter values of oxides studied in this work allows us to expect them to have similar sorption properties.\u003c/p\u003e \u003cp\u003eHowever, the obtained data on the porous characteristics of the studied oxides elucidated the differences in their morphology, which will certainly influence the process of sorption of repellents on their surface. In particular, Al\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e and SiO\u003csub\u003e2\u003c/sub\u003e C2 have approximately the same porosity, but due to the differences in the sorbent structure they have different specific surface area, which can greatly influence the rate of sorption, as well as desorption, of substances on their surface. ZrO\u003csub\u003e2\u003c/sub\u003e is another prime example. It has the lowest specific surface area among other studied in this work sorbents, while its average pore size is about 46 nm, suggesting its possible high sorption activity towards repellents. However, the structural advantages of different compounds do not always correlate with the expected experimental data on the sorption of substances.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec12\" class=\"Section2\"\u003e \u003ch2\u003eStatic sorption of DEET and IR3535\u003c/h2\u003e \u003cp\u003eThe results of static sorption of DEET and IR3535 on the surface of ZrO\u003csub\u003e2\u003c/sub\u003e, Al\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e, SiO\u003csub\u003e2\u003c/sub\u003e phenyl, SiO\u003csub\u003e2\u003c/sub\u003e C2 and SiO\u003csub\u003e2\u003c/sub\u003e 300 showed that all studied oxides possess sorption properties (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e). The biggest decrease in the concentration of compounds being sorbed within 360 min occurred on SiO\u003csub\u003e2\u003c/sub\u003e phenyl. The lowest repellent sorption capacity, despite high surface area values calculated by the BET method, was seen in SiO\u003csub\u003e2\u003c/sub\u003e 300. The obtained data suggest that both morphological parameters of the substances and their chemical nature are of particular importance in the sorption of DEET and IR3535.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe adsorption isotherms obtained after the establishment of equilibrium also clearly show the differences in the sorption of DEET and IR3535 onto the studied oxides (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e). Thus, SiO\u003csub\u003e2\u003c/sub\u003e phenyl demonstrates high sorption capacity for both repellents. At the same time, zirconium and aluminum oxides showed high values of adsorption capacity Q\u003csub\u003emax\u003c/sub\u003e (251 mg/g and 231 mg/g, respectively) in relation to IR3535 (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e). Such a difference in sorption of DEET and IR3535 for these oxides can be explained by the chemical structure of repellent molecules, which directly affects the mass transfer processes of substances. Pointedly, it was found that despite having the largest pore volume and high specific surface area (compared to the other studied oxides), SiO\u003csub\u003e2\u003c/sub\u003e C2 has a significantly inferior sorption capacity in respect to other oxides, in particular SiO\u003csub\u003e2\u003c/sub\u003e phenyl, which can be explained by the presence of the phenyl group in the latter that has chemical affinity for repellent molecules. Obtained isotherms of SiO\u003csub\u003e2\u003c/sub\u003e 300 also confirm the low sorption activity towards DEET, which can be explained by the structure of the repellent molecule.\u003c/p\u003e \u003cp\u003eThus, the sorption of DEET and IR3535 repellents does not directly depend on the morphology of the studied oxides. The study results showed that SiO\u003csub\u003e2\u003c/sub\u003e phenyl oxide has the highest sorption capacity for DEET (239 mg/g), while ZrO\u003csub\u003e2\u003c/sub\u003e, Al\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e, SiO\u003csub\u003e2\u003c/sub\u003e phenyl oxides \u0026ndash; for IR3535 (251;231;221 mg/g, respectively), which makes these compounds suitable for their further use as repellent carrier substances.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe most common isotherms (Langmuir, Freundlich, Temkin, Dubinin-Radushkevich, Hill-de Boer and Frumkin-Fowler-Guggenheim (FFG)) were chosen to describe in detail the static sorption of repellents on porous oxides and linear approximation parameters were calculated [\u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e]. Results presented in Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003e show that the sorption of DEET and IR3535 onto zirconium, aluminum and silicon oxides are better described by the Langmuir isotherm (Eq.\u0026nbsp;\u003cspan refid=\"Equ1\" class=\"InternalRef\"\u003e1\u003c/span\u003e), as indicated by the high values of the correlation coefficient (R\u003csup\u003e2\u003c/sup\u003e) compared to the other isothermal models. The values of the separation factor R\u003csub\u003eL\u003c/sub\u003e (0\u0026thinsp;\u0026lt;\u0026thinsp;R\u003csub\u003eL\u003c/sub\u003e \u0026lt;1), calculated by Eq.\u0026nbsp;\u003cspan refid=\"Equ2\" class=\"InternalRef\"\u003e2\u003c/span\u003e, indicate a shift of adsorption equilibrium towards the sorption process. At the same time, the sorption of DEET onto the SiO\u003csub\u003e2\u003c/sub\u003e phenyl surface is best described by the Freundlich model (Eq.\u0026nbsp;\u003cspan refid=\"Equ3\" class=\"InternalRef\"\u003e3\u003c/span\u003e). Withal, the sorption of DEET onto the SiO\u003csub\u003e2\u003c/sub\u003e phenyl surface is best described by the Freundlich model (Eq.\u0026nbsp;\u003cspan refid=\"Equ3\" class=\"InternalRef\"\u003e3\u003c/span\u003e). Values of the coefficient n\u0026thinsp;\u0026lt;\u0026thinsp;1 in this case indicate a chemical interaction between the sorbent and sorbate. For other sorption processes, values of the coefficient n\u0026thinsp;\u0026ge;\u0026thinsp;1 indicate that mainly the process physical sorption is happening. The Langmuir and Freundlich isotherm models are expressed by the following equations:\u003c/p\u003e \u003cp\u003eLangmuir isotherm\u003cdiv id=\"Equ1\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equ1\" name=\"EquationSource\"\u003e\n$$\\frac{1}{{Q}_{e}}= \\frac{1}{{Q}_{max}\\bullet {K}_{L}}\\frac{1}{{C}_{e}}+\\frac{1}{{Q}_{max}}$$\u003c/div\u003e\u003cdiv class=\"EquationNumber\"\u003e1\u003c/div\u003e\u003c/div\u003e\u003cdiv id=\"Equ2\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equ2\" name=\"EquationSource\"\u003e\n$${R}_{L}= \\frac{1}{1+{K}_{L}{C}_{e}}$$\u003c/div\u003e\u003cdiv class=\"EquationNumber\"\u003e2\u003c/div\u003e\u003c/div\u003e\u003c/p\u003e \u003cp\u003eFreundlich isotherm\u003cdiv id=\"Equ3\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equ3\" name=\"EquationSource\"\u003e\n$$ln{Q}_{e}= ln{K}_{f}+\\frac{1}{n}ln{C}_{e}$$\u003c/div\u003e\u003cdiv class=\"EquationNumber\"\u003e3\u003c/div\u003e\u003c/div\u003e\u003c/p\u003e \u003cp\u003ewhere Q\u003csub\u003ee\u003c/sub\u003e is the quantity adsorbed by the unit mass of the adsorbent (mg/g), Q\u003csub\u003emax\u003c/sub\u003e is the capacity of the adsorbent monolayer (mg/g), C\u003csub\u003ee\u003c/sub\u003e is the adsorbate equilibrium concentration (mg/L), K\u003csub\u003eL\u003c/sub\u003e is the Langmuir adsorption constant, K\u003csub\u003ef\u003c/sub\u003e and n are Freundlich constants where the value of 1/n indicates the degree of linearity of isotherm.\u003c/p\u003e \u003cp\u003eThe isothermal Temkin model (Eq.\u0026nbsp;\u003cspan refid=\"Equ4\" class=\"InternalRef\"\u003e4\u003c/span\u003e) allows us to determine the energy of sorbate-sorbent interaction on the oxide surface.\u003c/p\u003e \u003cp\u003eTemkin isotherm\u003cdiv id=\"Equ4\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equ4\" name=\"EquationSource\"\u003e\n$${Q}_{e}= {B}_{T}ln{A}_{T}+{B}_{T}ln{C}_{e}$$\u003c/div\u003e\u003cdiv class=\"EquationNumber\"\u003e4\u003c/div\u003e\u003c/div\u003e\u003c/p\u003e \u003cp\u003ewhere B\u003csub\u003eT\u003c/sub\u003e is the adsorption heat constant, and A\u003csub\u003eT\u003c/sub\u003e is the binding equilibrium constant.\u003c/p\u003e \u003cp\u003eFor all studied samples, the values of sorption heat B\u003csub\u003eT\u003c/sub\u003e of the repellents onto the considered sorbents were more than 8 kJ/mol, which may indirectly indicate the occurrence of chemosorption process. However, it is known that the Temkin model is valid only for certain linear sections and cannot be applied for the range of small and large values of concentrations, thus making it impossible to assess its applicability in full [\u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eThe occurrence of chemosorption process can be indirectly confirmed by the data calculated by the Dubinin-Radushkevich method, where the sorption energy of the sorbate E was more than 8 kJ/mol (Eq.\u0026nbsp;\u003cspan refid=\"Equ5\" class=\"InternalRef\"\u003e5\u003c/span\u003e\u0026ndash;\u003cspan refid=\"Equ6\" class=\"InternalRef\"\u003e6\u003c/span\u003e). This method is used to determine the mechanism of sorption with Gaussian energy distribution in heterogeneous systems.\u003c/p\u003e \u003cp\u003eDubinin-Radushkevich isotherm\u003cdiv id=\"Equ5\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equ5\" name=\"EquationSource\"\u003e\n$$lnQ=ln{Q}_{s}-\\left(\\beta {\\epsilon }^{2}\\right)$$\u003c/div\u003e\u003cdiv class=\"EquationNumber\"\u003e5\u003c/div\u003e\u003c/div\u003e\u003cdiv id=\"Equ6\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equ6\" name=\"EquationSource\"\u003e\n$$E= \\frac{1}{\\surd 2\\beta }$$\u003c/div\u003e\u003cdiv class=\"EquationNumber\"\u003e6\u003c/div\u003e\u003c/div\u003e\u003c/p\u003e \u003cp\u003ewhere β is the Dubinin-Radushkevich isotherm constant; Qs is theoretically calculated adsorption capacity, mg/g; ε is the Polanyi potential (J/mol), E is the adsorption energy per one molecule of adsorbate, i.e., the energy needed to remove a molecule from the adsorbate\u0026rsquo;s surface (kJ/mol).\u003c/p\u003e \u003cp\u003eLike Polanyi\u0026rsquo;s theory, the Dubinin-Radushkevich model is based on assumptions applicable for polymolecular sorption. At the same time, the obtained data suggests that primarily a monolayer formation of repellent molecules on porous oxides occurs. Moreover, relatively low values of the determination coefficient in this model (less than 0.95) for Al\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e, SiO\u003csub\u003e2\u003c/sub\u003e phenyl, SiO\u003csub\u003e2\u003c/sub\u003e C2 and SiO\u003csub\u003e2\u003c/sub\u003e 300 do not allow to consider this model for the studied systems.\u003c/p\u003e \u003cp\u003eThe Frumkin-Fowler-Guggenheim (FFG) model is used to describe the sorption process of various pollutants from water (Eq.\u0026nbsp;\u003cspan refid=\"Equ7\" class=\"InternalRef\"\u003e7\u003c/span\u003e) [\u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e31\u003c/span\u003e]. Frumkin adsorption isotherm for aqueous systems relates the occupancy of sorption sites \u003cem\u003eθ\u003c/em\u003e with the volume concentration \u003cem\u003eCe\u003c/em\u003e. Since this model is applicable to aqueous systems, we assumed it possible to apply it to elaborate our system, which comprised a solution of repellents in a polar solvent. This model allows us to calculate the binding energy of molecules to the solid sorbate [\u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eFrumkin-Fowler-Guggenheim isotherm\u003cdiv id=\"Equ7\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equ7\" name=\"EquationSource\"\u003e\n$${ln}\\left(\\frac{{C}_{e}\\left(1-\\theta \\right)}{\\theta }\\right)-\\frac{\\theta }{1-\\theta }=-ln{K}_{FG}+\\frac{2W\\theta }{RT}$$\u003c/div\u003e\u003cdiv class=\"EquationNumber\"\u003e7\u003c/div\u003e\u003c/div\u003e\u003c/p\u003e \u003cp\u003ewhere K\u003csub\u003eFG\u003c/sub\u003e \u0026ndash; isotherm constant, θ is a parameter used to describe the fraction of surface occupied by adsorbent molecules, W is the interaction energy between two adsorbed molecules on the adjacent neighboring site (kJ/mol), R is the gas constant (J/mol\u0026bull;K), Т is sorption temperature (K).\u003c/p\u003e \u003cp\u003eThe empirical sorption energy values were found to be negative W\u0026thinsp;\u0026lt;\u0026thinsp;0 for all studied processes, indicating a repellent effect between the molecules of the sorbed repellents.\u003c/p\u003e \u003cp\u003eSimilarly to the Frumkin-Fowler-Guggenheim model, the Hil-de Boer model (Eq.\u0026nbsp;\u003cspan refid=\"Equ8\" class=\"InternalRef\"\u003e8\u003c/span\u003e) can be used to describe sorption in heterogeneous systems containing polar solvents [\u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e]. The FFG model assumes a localized sorption process happening, while the Hil-de Boer model regards the formation of a mobile monolayer.\u003c/p\u003e \u003cp\u003eHil-de Boer isotherm\u003cdiv id=\"Equ8\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equ8\" name=\"EquationSource\"\u003e\n$${ln}\\left(\\frac{{C}_{e}\\left(1-\\theta \\right)}{\\theta }\\right)-\\frac{\\theta }{1-\\theta }=-ln{K}_{1}-\\frac{{K}_{2}\\theta }{RT}$$\u003c/div\u003e\u003cdiv class=\"EquationNumber\"\u003e8\u003c/div\u003e\u003c/div\u003e\u003c/p\u003e \u003cp\u003ewhere К\u003csub\u003e1\u003c/sub\u003e is the Hil-de Boer constant (L/mg), К\u003csub\u003e2\u003c/sub\u003e is the energetic constant of interaction between the adsorbed molecules (kJ/mol).\u003c/p\u003e \u003cp\u003eThe K\u003csub\u003e2\u003c/sub\u003e constant in the Hil-de Boer model describes the interaction energy of sorbate molecules on the sorbent surface. The values of constants for all studied sorption processes were negative, which also indicates repulsion of repellent molecules.\u003c/p\u003e \u003c/div\u003e"},{"header":"Conclusions","content":"\u003cp\u003eThis work is dedicated to the study of the sorption properties of zirconia, alumina and silicas towards repellents; the morphological properties of these compounds were determined using SEM and BET methods. The obtained results showed that the synthesized zirconium and aluminum oxides, as well as silicon oxides, possess a well-developed mesoporous structure with various specific surface areas (34\u0026ndash;380 g/m\u003csup\u003e2\u003c/sup\u003e).\u003c/p\u003e \u003cp\u003eThe sorption capacity of zirconium, aluminum and silicon oxides to the most widely used repellents, DEET and IR3535, was also studied. SiO\u003csub\u003e2\u003c/sub\u003e phenyl and Al\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e showed the best sorption capacity towards the DEET repellent (239 and 119 mg/g, respectively), while ZrO\u003csub\u003e2\u003c/sub\u003e, Al\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e, SiO\u003csub\u003e2\u003c/sub\u003e phenyl showed a significant sorption capacity towards the IR3535 repellent (251; 231 and 221 mg/g, respectively). Such a difference in the sorption of these compounds can be explained by both the morphology of the sorbents and the amino groups present in the DEET and IR3535 molecules. Moreover, the obtained results showed that the large specific area of the sorbents is not a determining factor in the sorption of the repellents. Despite this, SiO\u003csub\u003e2\u003c/sub\u003e phenyl and Al\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e can be further utilized to create repellent materials based on DEET and IR3535.\u003c/p\u003e \u003cp\u003eIsothermal models were used to calculate the parameters of repellent sorption onto ZrO\u003csub\u003e2\u003c/sub\u003e, Al\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e, SiO\u003csub\u003e2\u003c/sub\u003e phenyl, SiO\u003csub\u003e2\u003c/sub\u003e C2 and SiO\u003csub\u003e2\u003c/sub\u003e 300. It showed that this process is best described by the Langmuir model, which confirms that the maximum adsorption capacity is reached when a sorbent monolayer is formed.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eAcknowledgements\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe authors are grateful to the staff of the Nanyang Technological University (Singapore) and the staff of the Center for Instrumental Chemical Analysis and Complex Investigation of Substances and Materials of RTU MIREA (Russia) for their assistance in conducting physicochemical studies.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eFunding\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe work was carried out at the expense of the industry research program of Rospotrebnadzor for 2024-2025 (No.\u0026nbsp;1023032900395-5-1.6.23) and supported by Singapore MAR grant 04INS000458C150OOE01.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAuthor contributions\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eSergei. A. Zverev: Investigation, Original draft. Yana. V. Vinogradova: Investigation. Anna. A. Selivanova: Investigation. Roman. D. Solovov: Methodology, Resources. Konstantin. A. Sakharov: Visualization, Review \u0026amp; Editing. Anatoliy. A. Ischenko: Supervision. Sergei. V. Andreev: Original draft, Project administration.\u003c/p\u003e\n\u003cp\u003eAuthors declare not to have any conflicts of interest.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eEthical Approval\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eNot applicable\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAvailability of data and materials\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe manuscript reports the complete dataset. If needed, the corresponding author can be contacted via email for further calculations.\u003c/p\u003e\n"},{"header":"References","content":"\u003col\u003e\n\u003cli\u003eAnnandarajah C. et al. Biobased plastics with insect‐repellent functionality //Polymer Engineering \u0026amp; Science. 2019. V. 59. №. s2. P. E460-E467. https://doi.org/10.1002/pen.25083\u003c/li\u003e\n\u003cli\u003eda Silva M. R. M., Ricci-J\u0026uacute;nior E\u003cem\u003e.\u003c/em\u003e An approach to natural insect repellent formulations: from basic research to technological development //Acta tropica. 2020. V. 212. P. 105419. https://doi.org/10.1016/j.actatropica.2020.105419\u003c/li\u003e\n\u003cli\u003eNogueira Barradas T. et al. Polymer-based drug delivery systems applied to insects repellents devices: a review //Current drug delivery. 2016. V. 13. №. 2. P. 221-235.\u003c/li\u003e\n\u003cli\u003eWorld Health Organization. World malaria report 2022. \u0026ndash; World Health Organization, 2022.\u003c/li\u003e\n\u003cli\u003eClimate change and health [Electronic resource]. URL: https://www.who.int/news-room/fact-sheets/detail/climate-change-and-health.\u003c/li\u003e\n\u003cli\u003eEmam H. E., Abdelhameed R. M. In-situ modification of natural fabrics by Cu-BTC MOF for effective release of insect repellent (N, N-diethyl-3-methylbenzamide) //Journal of Porous Materials. 2017. V. 24. P. 1175-1185. https://doi.org/10.1007/s10934-016-0357-y\u003c/li\u003e\n\u003cli\u003eTavares M. et al\u003cem\u003e.\u003c/em\u003e Trends in insect repellent formulations: A review //International journal of pharmaceutics. 2018. V. 539. №. 1-2. P. 190-209. https://doi.org/10.1016/j.ijpharm.2018.01.046\u003c/li\u003e\n\u003cli\u003eDu F. et al. 3D-Printing of the polymer/insect-repellent system poly (L-lactic acid)/ethyl butylacetylaminopropionate (PLLA/IR3535) //International Journal of Pharmaceutics. 2022. V. 624. P. 122023. https://doi.org/10.1016/j.ijpharm.2022.122023\u003c/li\u003e\n\u003cli\u003eXiang C. et al. Structure and properties of polyamide fabrics with insect-repellent functionality by electrospinning and oxygen plasma-treated surface coating //Polymers. 2020. V. 12. №. 10. P. 2196. https://doi.org/10.3390/polym12102196\u003c/li\u003e\n\u003cli\u003eRichoux G. M. et al. Structure\u0026ndash;activity relationship analysis of potential new vapor-active insect repellents //Journal of Agricultural and Food Chemistry. 2020. V. 68. №. 47. P. 13960-13969. https://doi.org/10.1021/acs.jafc.0c03333\u003c/li\u003e\n\u003cli\u003ePaul R. (ed.). Functional finishes for textiles: improving comfort, performance and protection. Elsevier, 2014.\u003c/li\u003e\n\u003cli\u003eElsayed G. A., Hassabo A. G. Insect repellent of cellulosic fabrics (a review) //Letters in Applied NanoBioScience. 2022. V. 11. №. 1. P. 3181-3190. https://doi.org/10.33263/LIANBS111.31813190\u003c/li\u003e\n\u003cli\u003eSong J. Y., Bhadra B. N., Jhung S. H. Contribution of H-bond in adsorptive removal of pharmaceutical and personal care products from water using oxidized activated carbon //Microporous and Mesoporous Materials. 2017. V. 243. P. 221-228. https://doi.org/10.1016/j.micromeso.2017.02.024\u003c/li\u003e\n\u003cli\u003eTrouv\u0026eacute; A. et al. Tuning the hydrophobicity of mesoporous silica materials for the adsorption of organic pollutant in aqueous solution //Journal of hazardous materials. 2012. V. 201. P. 107-114. https://doi.org/10.1016/j.jhazmat.2011.11.043\u003c/li\u003e\n\u003cli\u003eMarocco A. et al. Removal of Agrochemicals from Waters by Adsorption: A Critical Comparison among Humic-Like Substances, Zeolites, Porous Oxides, and Magnetic Nanocomposites //Processes. 2020. V. 8. №. 2. P. 141. https://doi.org/10.3390/pr8020141\u003c/li\u003e\n\u003cli\u003eBlachnio M. et al.\u003cem\u003e \u003c/em\u003eAdsorption of Phenoxyacetic Herbicides from Water on Carbonaceous and Non-Carbonaceous Adsorbents //Molecules. 2023. V. 28. №. 14. P. 5404. https://doi.org/10.3390/molecules28145404\u003c/li\u003e\n\u003cli\u003eWang L. et al. Rational design, synthesis, adsorption principles and applications of metal oxide adsorbents: a review //Nanoscale. 2020. V. 12. №. 8. P. 4790-4815. https://doi.org/10.1039/C9NR09274A\u003c/li\u003e\n\u003cli\u003eRavindhranath K., Ramamoorty M. Nano aluminum oxides as adsorbents in waterremediation methods: a review //Rasayan J. Chem. 2017. V. 10. P. 716-722. http://dx.doi.org/10.7324/RJC.2017.1031762\u003c/li\u003e\n\u003cli\u003eZotov R. et al. Influence of the composition, structure, and physical and chemical properties of aluminium-oxide-based sorbents on water adsorption ability //Materials. 2018. V. 11. №. 1. P. 132. https://doi.org/10.3390/ma11010132\u003c/li\u003e\n\u003cli\u003eReshetnikov S. et al. Effect of particle size on adsorption kinetics of water vapor on porous aluminium oxide material //Journal of Physics: Conference Series. IOP Publishing, 2019. V. 1145. №. 1. P. 012033. https://doi.org/10.1088/1742-6596/1145/1/012033\u003c/li\u003e\n\u003cli\u003eYoussef W. M., Hagag M. S., Ali A. H\u003cem\u003e.\u003c/em\u003e Synthesis, characterization and application of composite derived from rice husk ash with aluminium oxide for sorption of uranium //Adsorption Science \u0026amp; Technology. 2018. V. 36. №. 5-6. P. 1274-1293. https://doi.org/10.1177/0263617418768920\u003c/li\u003e\n\u003cli\u003eHussain T. et al. Biogenic synthesis of date stones biochar-based zirconium oxide nanocomposite for the removal of hexavalent chromium from aqueous solution //Applied Nanoscience. 2022. P. 1-14. https://doi.org/10.1007/s13204-022-02599-z\u003c/li\u003e\n\u003cli\u003eDubey S. S., Grandhi S. Sorption studies of yttrium (III) ions on surfaces of nano-thorium (IV) oxide and nano-zirconium (IV) oxide //International Journal of Environmental Science and Technology. 2019. V. 16. P. 59-70. https://doi.org/10.1007/s13762-017-1589-3\u003c/li\u003e\n\u003cli\u003eAbass M. R., El-Kenany W. M., Eid M. A. Sorption of cesium and gadolinium ions onto zirconium silico antimonate sorbent from aqueous solutions //Applied Radiation and Isotopes. 2023. V. 192. P. 110542. https://doi.org/10.1016/j.apradiso.2022.110542\u003c/li\u003e\n\u003cli\u003eRahman N., Varshney P., Nasir M\u003cem\u003e.\u003c/em\u003e Synthesis and characterization of polydopamine/hydrous zirconium oxide composite and its efficiency for the removal of uranium (VI) from water //Environmental Nanotechnology, Monitoring \u0026amp; Management. 2021. V. 15. P. 100458. https://doi.org/10.1016/j.enmm.2021.100458\u003c/li\u003e\n\u003cli\u003eShen D. et al. Fabricating ultrafine zirconium oxide based composite sorbents in \u0026ldquo;soft confined space\u0026rdquo; for efficiently removing fluoride from environmental water //Chemical Engineering Journal. 2022. V. 444. P. 136199. https://doi.org/10.1016/j.cej.2022.136199\u003c/li\u003e\n\u003cli\u003eRezaee S., Ranjbar K., Kiasat A. R. The effect of surfactant on the sol\u0026ndash;gel synthesis of alumina-zirconia nanopowders //Ceramics International. 2018. V. 44. №. 16. P. 19963-19969. https://doi.org/10.1016/j.ceramint.2018.07.263\u003c/li\u003e\n\u003cli\u003eBardestani R., Patience G. S., Kaliaguine S. Experimental methods in chemical engineering: specific surface area and pore size distribution measurements\u0026mdash;BET, BJH, and DFT //The Canadian Journal of Chemical Engineering. 2019. V. 97. №. 11. P. 2781-2791. https://doi.org/10.1002/cjce.23632\u003c/li\u003e\n\u003cli\u003e\u003cem\u003e \u003c/em\u003eRagadhita R., Nandiyanto A. B. D.\u003cem\u003e \u003c/em\u003eHow to calculate adsorption isotherms of particles using two-parameter monolayer adsorption models and equations //Indonesian Journal of Science and Technology. 2021. V. 6. №. 1. P. 205-234. https://doi.org/10.17509/ijost.v6i1.32354\u003c/li\u003e\n\u003cli\u003eChu K. H. Revisiting the Temkin isotherm: Dimensional inconsistency and approximate forms //Industrial \u0026amp; Engineering Chemistry Research. 2021. V. 60. №. 35. P. 13140-13147. https://doi.org/10.1021/acs.iecr.1c01788\u003c/li\u003e\n\u003cli\u003e\u003cem\u003e \u003c/em\u003eChu K. H., Tan B. C. Is the Frumkin (Fowler\u0026ndash;Guggenheim) adsorption isotherm a two-or three-parameter equation? //Colloid and Interface Science Communications. 2021. V. 45. \u0026ndash; P. 100519. https://doi.org/10.1016/j.colcom.2021.100519\u003c/li\u003e\n\u003cli\u003eTovbin Y. K. The Molecular Theory of Adsorption in Porous Solids. // CRC Press. 2017\u003c/li\u003e\n\u003cli\u003eChu K. H. et al. S-shaped adsorption isotherms modeled by the Frumkin\u0026ndash;Fowler\u0026ndash;Guggenheim and Hill\u0026ndash;de Boer equations //Monatshefte f\u0026uuml;r Chemie-Chemical Monthly. 2023. P. 1-9. https://doi.org/10.1007/s00706-023-03116-w.\u003c/li\u003e\n\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":"colloid-and-polymer-science","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"","sideBox":" Learn more about [Colloid and Polymer Science](https://www.springer.com/journal/396) ","snPcode":"396","submissionUrl":"https://mc.manuscriptcentral.com/cps","title":"Colloid and Polymer Science","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"Sorption, Alumina, Zirconia, Silica, Repellents, Isothermal models","lastPublishedDoi":"10.21203/rs.3.rs-3972861/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-3972861/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"In this work, the morphology of zirconia, alumina, and silicas was studied and static sorption of the repellents N,N-diethyl-3-methylbenzamide and ethyl-3-[acetyl(butyl)amino]propionate on these oxides was carried out. ZrO2, Al2O3, SiO2 phenyl were shown to have high sorption activity to the repellents N,N-diethyl-3-methylbenzamide (239 mg/g for SiO2 phenyl) and ethyl-3-[acetyl(butyl)amino]propionate (251 mg/g for ZrO2). Pointedly, it was found that despite having the largest pore volume and high specific surface area (compared to the other studied oxides), SiO2 C2 has a significantly inferior sorption capacity in respect to other oxides, in particular SiO2 phenyl, which can be explained by the presence of the phenyl group in the latter that has chemical affinity for repellent molecules. Obtained isotherms of SiO2 300 also confirm the low sorption activity towards N,N-diethyl-3-methylbenzamide. The sorption equilibrium for both repellents, in most cases, is described by the Langmuir monomolecular adsorption model. The obtained results suggest that the studied zirconia, alumina, and silica can be used as carrier components of repellents.","manuscriptTitle":"Study of sorption properties of zirconia, alumina and silica in relation to repellents","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2024-02-27 21:09:41","doi":"10.21203/rs.3.rs-3972861/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Revision requested","date":"2024-04-03T06:06:15+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2024-04-01T15:35:50+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"80be20bd-2e33-44e1-b5ea-1b64c2c53068","date":"2024-03-22T08:38:45+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2024-03-22T04:07:25+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2024-02-23T05:14:07+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2024-02-23T05:14:07+00:00","index":"","fulltext":""},{"type":"submitted","content":"Colloid and Polymer Science","date":"2024-02-20T13:15:32+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"colloid-and-polymer-science","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"","sideBox":" Learn more about [Colloid and Polymer Science](https://www.springer.com/journal/396) ","snPcode":"396","submissionUrl":"https://mc.manuscriptcentral.com/cps","title":"Colloid and Polymer Science","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"c475d24c-90ad-40ea-b4fe-a1e91eb382b5","owner":[],"postedDate":"February 27th, 2024","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[],"tags":[],"updatedAt":"2024-07-22T08:02:47+00:00","versionOfRecord":{"articleIdentity":"rs-3972861","link":"https://doi.org/10.1007/s00396-024-05260-z","journal":{"identity":"colloid-and-polymer-science","isVorOnly":false,"title":"Colloid and Polymer Science"},"publishedOn":"2024-05-16 08:02:47","publishedOnDateReadable":"May 16th, 2024"},"versionCreatedAt":"2024-02-27 21:09:41","video":"","vorDoi":"10.1007/s00396-024-05260-z","vorDoiUrl":"https://doi.org/10.1007/s00396-024-05260-z","workflowStages":[]},"version":"v1","identity":"rs-3972861","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-3972861","identity":"rs-3972861","version":["v1"]},"buildId":"qtupq5eGEP_6zYnWcrvyt","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}