Micro- and nanocellulose-based silica hybrid nanocomposites as eco-sorbents for efficient oil removal

Micro- and nanocellulose-based silica hybrid nanocomposites as eco-sorbents for efficient oil removal | 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 Micro- and nanocellulose-based silica hybrid nanocomposites as eco-sorbents for efficient oil removal Doniyor Jabborovich Ergasheva This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-9245876/v1 This work is licensed under a CC BY 4.0 License Status: Under Review Version 1 posted 5 You are reading this latest preprint version Abstract The synthesis of hydrophobic cellulose–silica composites was accomplished via a sol–gel route. Cellulose obtained from industrial licorice-root waste, an inexpensive raw material, was used as a renewable precursor in its microcrystalline (MCC) and nanocrystalline (NCC) forms. Methyltrimethoxysilane (MTMS) was employed as the silicon source as well as the hydrophobic modifying agent. During the study, the effects of the MCC and NCC/MTMS molar ratio, reaction temperature, and reaction time on composite formation were systematically investigated. The results showed that a molar ratio of MCC and NCC/MTMS of 1:1.8, a reaction temperature of 80–100°C, and a reaction duration of 60 minutes represented the optimal conditions for composite formation. The composites synthesized under these optimized parameters exhibited pronounced hydrophobic properties. The water contact angles of pristine microcrystalline cellulose (MCC) and nanocrystalline cellulose (NCC) were determined to be 15° ± 1°, indicating their intrinsically hydrophilic nature. In contrast, after silica modification, the water contact angle increased significantly to 120° ± 1° for the MCC–(CH₃SiO₁.₅)ₙ composite and to 136° ± 1° for the NCC–(CH₃SiO₁.₅)ₙ composite, confirming the successful formation of hydrophobic surfaces. Furthermore, benzene adsorption isotherms were investigated to evaluate the adsorption performance of the materials. At a relative pressure of P/P₀ = 1, the adsorption capacity of pristine MCC and NCC was found to be 0.88 cm³/g and 0.26 cm³/g, respectively. After composite formation, these values increased markedly to 5.3 cm³/g for the MCC–(CH₃SiO₁.₅)ₙ composite and 1.8 cm³/g for the NCC–(CH₃SiO₁.₅)ₙ composite, demonstrating a substantial enhancement in adsorption capacity as a result of silica incorporation and surface hydrophobization. The structural and thermal properties were evaluated using X-ray diffraction (XRD), thermogravimetric analysis (TGA), and Fourier-transform infrared spectroscopy (FTIR). Additionally, the hydrophobicity and oil/grease adsorption efficiency were assessed. The resulting materials exhibited enhanced water repellency, high thermal stability, and superior adsorption capacity for oil and grease. The utilization of cellulose–silica composites as sustainable adsorbents for the remediation of hydrocarbon-based pollutants is a promising avenue for environmental restoration. These composites are notable for their eco-friendly origin and demonstrated efficacy, which underscores their significant potential in addressing environmental concerns. Cellulose nanocrystals microcrystalline cellulose cellulose–silica composites sol–gel hybrid materials surface modification eco-sorbents Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 Figure 9 Introduction The drive to consume more energy is leading to a sharp increase in oil-contaminated wastewater Failures in transportation and processing systems—and disasters at sea involving tankers—have led to catastrophic pollution. This contamination hits marine ecosystems hardest and may cause long-term damage, including the loss of vulnerable species. [ 1 – 4 ]. Environmental protection from oil and grease contamination represents one of the most pressing ecological challenges. Hydrocarbon pollution of marine waters, particularly by oil and grease, has become a serious global concern [ 5 – 9 ]. Among the available technologies for oily wastewater treatment, membrane separation has attracted increasing attention due to its simplicity, energy efficiency, environmental safety, high separation performance, and cost-effectiveness [ 10 – 14 ]. It is widely recognized that oily effluents carry organics of intricate composition, elevated biotoxicity, and low biodegradability [ 15 ]. Hydrophobic and oleophilic materials play a pivotal role in tackling this issue, especially when derived from natural and renewable resources, as they are both eco-friendly and effective [ 16 – 18 ]. Among potential precursors for sorbent synthesis, cellulose derivatives and silica compounds stand out as highly promising candidates, particularly when combined through sol–gel synthesis [ 19 – 22 ]. Cellulose, the most abundant and renewable natural polymer, has gained remarkable attention in its modified forms such as microcrystalline cellulose (MCC) and nanocrystalline cellulose (NCC) [ 23 – 28 ]. As a key structural component of plants, cellulose exhibits high absorbency, mechanical strength, and biodegradability, which make it suitable for different applications [ 29 , 30 ]. However, the inherent hydrophilicity of native cellulose restricts its ability to remove hydrophobic contaminants such as oil and grease from aqueous media, highlighting the necessity of hydrophobic modification [ 31 , 32 ]. Silica-based compounds, in turn, are well known for their thermal stability as well as unique optical, electronic, and mechanical properties, which underpin their wide range of applications [ 33 ]. The silica surface is rich in silanol groups (Si–OH), which are hydrophilic yet chemically reactive, allowing for hydrophobic functionalization [ 34 , 35 ]. Through covalent bonding with organic molecules, silica can be converted into organic–inorganic hybrid materials with applications in sensors, catalysts, adsorbents, and biomaterials [ 36 , 37 ]. Cellulose–silica composites can be synthesized by three main approaches: the sol–gel method, layer-by-layer assembly, and biomineralization-inspired techniques [ 38 – 40 ]. Among these, the sol–gel route is the most widely employed, as it enables molecular-level control over material composition and microstructure under mild and low-energy conditions. Typical precursors include methyltrimethoxysilane (MTMS), tetraethoxysilane (TEOS), and tetramethoxysilane (TMOS), which undergo hydrolysis to form reactive silanol groups that condense into a stable silica network (gel). The resulting silica surface, rich in chemically active silanol groups, offers versatile opportunities for further functionalization [ 41 – 44 ]. In this context, the present study focuses on the development of hydrophobic cellulose–silica composite materials synthesized via the sol–gel method. Cellulose obtained from industrial licorice-root waste, an inexpensive raw material, was used as a renewable precursor in its microcrystalline (MCC) and nanocrystalline (NCC) forms. Methyltrimethoxysilane (MTMS) was employed as the silicon source as well as the hydrophobic modifying agent. During condensation, MTMS retains the –CH₃ group within the resulting silica network. The –CH₃ functional group is an organic radical characterized by low polarity, low dielectric constant, and strong Van der Waals interactions (similar to hydrocarbons), which converts the structure into an organically modified silica and inherently imparts hydrophobicity. In contrast, silica derived from TEOS/TMOS generally exhibits hydrophilic properties. The objectives of the study were to investigate the influence of key synthesis parameters, including MCC/MTMS molar ratio, reaction temperature, and reaction time, on the formation of cellulose–silica composites; characterize the morphology, structure, and thermal stability of the obtained materials using XRD, FTIR, and TGA; and evaluate the hydrophobicity and sorption performance of the composites toward oil and grease. The findings are expected to provide valuable insights into the design of eco-friendly, bio-based hybrid sorbents for efficient treatment of oily wastewater and environmental remediation. Materials and Methods Materials Microcrystalline cellulose (MCC) with a degree of crystallinity of 69% and a degree of polymerization of 350–400, and nanocrystalline cellulose (NCC) with a degree of crystallinity of 78% and a degree of polymerization of 150–250, were derived from licorice root cellulose extracted in our previous study. Methyltrimethoxysilane (MTMS, ≥ 98%, CAS No. 1185-55-3), Sulphuric acid (H₂SO₄, CAS No. 7664-93-9), ethanol (C 2 H 5 OH, ≥ 95%, CAS No. 61-73-4), Nitrite acid (HNO₃, CAS No. 7697-37-2), hydrochloric acid (HCl, 0.1 N, CAS No. 7647-01-0), and ammonium hydroxide (NH₄OH, 0.1 N, CAS No. 1336-21-6) were purchased from commercial suppliers (Sigma-Aldrich, China) and used without further purification. Distilled water was used throughout all experiments. Sample Preparation Preparation of Nanocrystalline Cellulose (NCC) NCC was prepared by the previously method [ 45 ] using acid hydrolysis of licorice root cellulose in 55% H₂SO₄ at 50°C, maintaining a cellulose-to-acid ratio of 1:10 (w/v). The reaction was conducted for 90 min under constant stirring, followed by dilution with cold water, centrifugation, and repeated washing until neutrality was achieved. Preparation of Microcrystalline Cellulose (MCC) MCC was obtained by the previously method [ 45 ] from licorice root cellulose by hydrolysis in a 4% HNO₃ solution in an autoclave at 100–110°C for 60 minutes, using a cellulose-to-acid ratio of 1:10 (w/v). The resulting product was filtered, thoroughly washed with distilled water until a neutral pH was reached, and dried at 100–105°C. Synthesis of Cellulose–Silica Composites (CSC) Cellulose suspensions were prepared by dispersing 1.05 g of either MCC or NCC in 10 mL of ethanol, followed by homogenization using an IKA Ultra-Turrax Tube Disperser (Germany) at 5000 rpm for 1 h. For the hydrolysis of MTMS, 2 mL of MTMS was mixed with 2 mL of ethanol (95%) and 1 mL of HCl (0.1 N) at room temperature. The mixture was stirred at 500 rpm for 1 h to generate reactive silanol groups. In the subsequent step, the cellulose suspension was added dropwise to the hydrolyzed MTMS solution under continuous stirring. After 10 min, 1 mL of 0.1 N NH₄OH was added to initiate the gelation process, and the mixture was further stirred at 500 rpm for an additional 1 h. The resulting gel was washed several times with distilled water and ethanol, and then dried at 100–105°C. For comparison with the composite materials, pure methyl silicate salt was synthesized. For the hydrolysis of MTMS, 2 mL of MTMS was mixed with 2 mL of 95% ethanol and 1 mL of 0.1 N HCl at room temperature. The resulting mixture was stirred at 500 rpm for 1 h to generate reactive silanol groups. Subsequently, to initiate the condensation process, 1 mL of 0.1 N NH₄OH was added to the hydrolyzed MTMS solution, and the mixture was further stirred at 500 rpm for an additional 1 h. The resulting gel was washed several times with distilled water and ethanol, and then dried at 100–105°C. Characterization Fourier-transform infrared spectroscopy (FTIR) Spectra were recorded on a Bruker Inventio-S IR spectrometer (Germany) in the range 500–4000 cm⁻¹. X-ray diffraction (XRD) Analysis was performed using a Rigaku Miniflex 600 diffractometer (Japan) with monochromatic CuKα radiation (λ = 1.5418 Å, Ni filter). Operating conditions: 40 kV, 15 mA; scan range: 2θ = 5–40°. Data analysis involved peak deconvolution, Miller indexing, and amorphous content quantification using SmartLab Studio II and the ICDD PDF-2 (2020) database. Thermogravimetric analysis (TGA) Conducted with a Linseis STA TG-DTA/DSC “Start-1600” system (Germany) under air atmosphere, heating rate 10°C/min, within the range 20–800°C. Water contact angle (WCA) The hydrophobicity of the composites was evaluated by static water contact angle measurements using a Drop Shape Analyzer – DSA25 (KRÜSS GmbH, Germany) A 5 µL deionized water droplet was placed on the composite surface, and images were captured after 10 s. Reported values represent the average of at least five independent measurements. The technical specifications of the DSA25 indicate that the sessile (static) droplet method allows measurements in the range of 0°–180°. The reported accuracy is given as approximately 0.1° to 1°. Benzene sorption isotherm studies The benzene vapor adsorption capacity of the samples was determined using a volumetric adsorption analyzer, Autosorb iQ (Anton Paar, Austria). Prior to analysis, the samples (≈ 100 mg) were degassed under vacuum at 60°C for 12 h to remove physically adsorbed moisture. Adsorption isotherms were recorded at 25°C over a relative pressure (P/P₀) range of 0.05–0.95. The equilibrium sorption capacity was calculated based on the amount of adsorbed benzene vapor per unit mass of the dried sample. Statistical analysis All experimental data were collected in triplicates and data expressed as the mean ± standard deviation. Data were compared using a one-way ANOVA with post-Bonferroni test using GraphPad Prism 5.04 (GraphPad Software Inc., San Diego, California), with p < 0.05 depicting significant difference between data sets Results and Discussion FTIR Spectroscopy Analysis The FTIR spectra of pristine microcrystalline cellulose (MCC) and nanocrystalline cellulose (NCC) (curves 1 and 2) exhibit characteristic absorption bands typical of cellulose. The broad band observed in the range of 3350–3450 cm⁻¹ is attributed to the stretching vibrations of hydroxyl (–OH) groups, indicating the presence of strong intermolecular and intramolecular hydrogen bonding within the cellulose structure. The absorption bands around 2900 cm⁻¹ correspond to the C–H stretching vibrations of aliphatic –CH and –CH₂ groups. The band located near 1640 cm⁻¹ is associated with the bending vibrations of adsorbed water molecules. In addition, the bands in the 1000–1150 cm⁻¹ region are assigned to the stretching vibrations of C–O–C and C–O bonds of the pyranose ring, confirming the polysaccharide backbone of cellulose. The FTIR spectrum of pristine metilsiloksan ((CH₃SiO₁.₅)ₙ) displays well-defined absorption bands in the range of 1080–1100 cm⁻¹, which are mainly attributed to the asymmetric stretching vibrations of Si–O–Si bonds within the siloxane network. The band observed around 800 cm⁻¹ corresponds to the symmetric stretching vibrations of Si–O–Si bonds, while the absorption near 460 cm⁻¹ is associated with the bending vibrations of the siloxane framework [ 46 – 48 ]. Furthermore, the presence of absorption bands in the range of 1270–1260 cm⁻¹ is assigned to the stretching vibrations of Si–CH₃ bonds, indicating the retention of methyl groups within the siloxane network. The bands observed in the 2970–2850 cm⁻¹ region are attributed to the C–H stretching vibrations of methyl groups. These spectral features confirm that the methyl silicate salt possesses an organically modified siloxane structure, accounting for its low polarity and inherent hydrophobic characteristics. The FTIR spectra of the MCC–(CH₃SiO₁.₅)ₙ and NCC–(CH₃SiO₁.₅)ₙ composites (curves 3 and 4) exhibit combined features characteristic of both cellulose and silica, confirming the successful formation of hybrid composites. The reduced intensity of the –OH stretching band in the 3350–3450 cm⁻¹ region compared to pristine cellulose indicates the occurrence of condensation reactions between the hydroxyl groups of cellulose and the silanol groups generated from MTMS. The appearance and enhancement of absorption bands in the 1000–1100 cm⁻¹ region are attributed to the overlapping stretching vibrations of Si–O–Si and Si–O–C bonds, providing strong evidence for the formation of covalent linkages between the cellulose matrix and the silica network. Moreover, the presence of absorption bands in the 2970–2850 cm⁻¹ region, along with weak bands observed at 1270–1260 cm⁻¹ in the composite samples, are associated with the stretching vibrations of Si–CH₃ bonds originating from MTMS, indicating that methyl groups are retained within the silica structure. These organic moieties lead to the formation of organically modified silica and significantly enhance the hydrophobic properties of the composites. Overall, the FTIR analysis clearly demonstrates that silica was successfully integrated into the cellulose structure via the sol–gel process and that effective surface modification was achieved using MTMS. The formation of Si–O–Si and Si–O–C bonds, together with the retention of –CH₃ groups, confirms the development of cellulose–silica composites with tailored structural and surface properties and markedly enhanced hydrophobicity. XRD Analysis To further investigate and compare the amorphous and crystalline structures of cellulose–silica composites, X-ray diffraction (XRD) analysis was performed Fig. 2 . The X-ray diffraction (XRD) patterns of the samples synthesized based on MTMS were investigated in order to evaluate the crystalline structure of cellulose and the structural influence of the methylsiloxane phase. The diffractograms of pure nanocrystalline cellulose (NC, curve 1) and microcrystalline cellulose (MCC, curve 2) exhibited sharp and intense diffraction peaks characteristic of cellulose I. The main diffraction peak located at 2θ ≈ 22–23° corresponds to the (200) crystallographic plane, while additional peaks observed in the 2θ ≈ 14–16° range are attributed to the (1̅10) and (110) planes. Based on crystallinity index calculations, the CrI value of the NC sample was determined to be 78%, whereas that of the MCC sample was 69%, indicating a higher degree of crystallinity for nanocrystalline cellulose. The diffractogram of pure methylsiloxane ((CH₃SiO₁.₅)ₙ, curve 5) showed no distinct crystalline diffraction peaks; instead, a broad, low-intensity halo centered at 2θ ≈ 20–25° was observed, confirming the amorphous nature of the siloxane network. This result indicates that the methylsiloxane phase derived from MTMS does not form a long-range ordered crystalline structure. In the diffractograms of the NC–(CH₃SiO₁.₅)ₙ and MCC–(CH₃SiO₁.₅)ₙ composites (curves 3 and 4), the main cellulose-related diffraction peaks were preserved; however, their intensities were significantly reduced compared to those of the pristine NC and MCC samples. The crystallinity index decreased sharply to 32% for NC–(CH₃SiO₁.₅)ₙ and 28% for MCC–(CH₃SiO₁.₅)ₙ. This pronounced reduction indicates that the incorporation of the methylsiloxane phase into the cellulose matrix disrupts the regular arrangement of cellulose chains and leads to partial destruction of the ordered crystalline domains. Table 1 Crystallinity index of NCC, MCC, and CSC samples Sample Crystallinity index (CrI, %) MCC 69 NCC 78 MCC–(CH₃SiO₁.₅)ₙ 28 NCC–(CH₃SiO₁.₅)ₙ 32 Thermogravimetric Analysis Figure 3 presents the thermogravimetric (TG) curves of MCC, NCC, and their cellulose–silica composites, illustrating the influence of silica incorporation on thermal stability. The TGA profiles of all samples reveal a three-step weight-loss behavior. The first stage, observed between 60–150°C, corresponds to the removal of physically adsorbed moisture. This is a typical feature of cellulose-based materials due to their inherent hydrophilicity. The second stage corresponds to the principal thermal degradation of cellulose, and its temperature range depends on the sample composition. For pure MCC, degradation occurs within 295–315°C, while for MCC–(CH₃SiO₁.₅)ₙ composites this range shifts upward to 305–345°C. Similarly, pure NCC decomposes at ~ 300–330°C, whereas NCC–(CH₃SiO₁.₅)ₙ composites exhibit delayed degradation between 325–375°C. This noticeable increase in decomposition temperature indicates a significant enhancement in thermal stability upon hybridization. The improvement can be attributed to strong hydrogen bonding and possible covalent interactions between cellulose hydroxyl groups and silica silanols, which restrict polymer chain mobility and slow down thermal decomposition [ 49 ]. The third stage corresponds to complete decomposition of the cellulose fraction, leaving behind a silica-rich residue. The higher char yield observed in CSC compared to pristine cellulose further confirms the successful integration of thermally stable inorganic silica into the organic matrix. Overall, the incorporation of silica substantially improves the thermal stability of cellulose, broadening the operational temperature window of the composites. These results emphasize the potential of cellulose–silica hybrids for high-temperature applications such as flame-retardant coatings, thermal insulation materials, and structural eco-composites [ 50 , 51 ]. Effect of MTMS content on water contact angle (WCA) To evaluate the effect of MTMS concentration on the hydrophobicity of cellulose–silica composites, WCA measurements were carried out at various cellulose/MTMS molar ratios Fig. 4 . The experiments were performed using either MCC or NCC as the substrate. When MCC and NCC were used as cellulose sources, increasing the MTMS ratio relative to 1 mol of cellulose led to a gradual increase in WCA. For MCC-based composites, the WCA increased from 5° (1:1 and 1:1.2) to 40° (1:1.4), 80° (1:1.6), 100° (1:1.8), and finally 110° (1:2). In contrast, under the same conditions, NCC-based composites exhibited a much stronger hydrophobic response, with WCA values of 5° (1:1), 28° (1:1.2), 63° (1:1.4), 106° (1:1.6), 125° (1:1.8), and 126° (1:2), respectively.These results clearly demonstrate that increasing MTMS content enhances hydrophobicity in both MCC- and NCC -based systems, but the effect is more pronounced for NCC. The superior performance of NCC composites can be attributed to their higher specific surface area and nanoscale porosity, which provide more active sites for silanol condensation and siloxane network formation. As a result, NCC enables denser and more uniform hydrophobic surface coverage compared to MCC. Notably, at cellulose-to-MTMS ratios of 1:1.8 and 1:2, the WCA values approach saturation, indicating that surface functionalization is nearly complete. For MCC, WCA values stabilized at ~ 100–110°, whereas CNC achieved values as high as 125–126°, consistent with previously reported sol–gel modified cellulose systems [ 52 ]. These findings underscore the critical role of cellulose morphology in determining the efficiency of silane grafting and the final hydrophobic performance of biocomposites. Effect of reaction temperature on water contact angle To further investigate the influence of synthesis parameters on hydrophobicity, experiments were conducted at a fixed cellulose-to-MTMS molar ratio of 1:1.8 while systematically varying the reaction temperature from 20 to 100°C (20, 40, 60, 80, and 100°C). The hydrophobicity of MCC–SiO₂ and NCC –SiO₂ composites was evaluated by measuring static water contact angles Fig. 5 . The WCA values increased progressively with temperature for both MCC- and NCC-based composites. This behaviour indicates that elevated reaction temperatures promote the condensation of hydrolyzed MTMS silanol groups with cellulose hydroxyl functionalities, leading to the formation of a denser and more uniform siloxane network. The NCC -based composites exhibited the highest hydrophobicity, reaching a maximum WCA of 136°± 1°, whereas MCC-based composites achieved a lower maximum of 120°± 1°. The superior performance of NCC is attributed to its higher surface-to-volume ratio, nanoscale porosity, and abundance of active hydroxyl groups, all of which facilitate more efficient surface functionalization and silane grafting. In contrast, MCC possesses fewer accessible sites, resulting in a less extensive siloxane network. Effect of reaction time on water contact angle To complement these findings, the effect of reaction time was examined under optimized conditions (cellulose-to-MTMS ratio of 1:1.8 and temperature range of 80–100°C). The reaction time was varied from 30 to 120 min to evaluate the kinetics of surface modification Fig. 6 . The experimental results revealed that extending the reaction duration beyond 60 min had only a minimal effect on WCA, with differences of ~ 1–2°. This indicates that the majority of MTMS condensation occurs within the initial 30–60 min, after which the surface becomes nearly saturated with hydrophobic groups. Therefore, a reaction time of 30–60 min was identified as sufficient to achieve stable and effective hydrophobic modification. This not only improves time and energy efficiency but also enhances the practicality of the process for potential industrial-scale applications. Accordingly, subsequent experiments were carried out using 30 and 60 min as the standard reaction durations. Time-dependent stability of water contact angle To evaluate the stability of surface hydrophobicity, the time-dependent change in WCA was investigated for composites obtained under optimized synthesis conditions and compared with their corresponding MCC and NCC precursors Fig. 7 . For pristine MCC, the initial contact angle was only 15°± 1°, which decreased rapidly to ~ 3° within 20 min, indicating that the water droplet was quickly absorbed due to the strongly hydrophilic character of the cellulose surface. A similar trend was observed for NCC, where the initial contact angle of 15° ± 1° dropped to ~ 3° within 20 min, again reflecting its intrinsic hydrophilicity. In contrast, the cellulose–silica composites demonstrated markedly different behavior. The MCC–(CH₃SiO₁.₅)ₙ composite exhibited an initial WCA of 120°± 1°, which gradually decreased to 90° after 100 min. This result confirms that silica incorporation successfully imparted hydrophobicity to MCC, significantly reducing water absorption. Even more pronounced hydrophobic stability was observed in the NCC–(CH₃SiO₁.₅)ₙ composite: its initial WCA of 136°± 1° decreased only to 120°± 1° after 100 min, indicating a highly stable hydrophobic surface. These findings demonstrate that while pristine cellulose precursors are strongly hydrophilic, their corresponding silica-based composites retain long-term hydrophobicity. The superior performance of NCC–(CH₃SiO₁.₅)ₙ composites can be attributed to their higher surface area, nanoscale porosity, and more efficient silane grafting, which together provide a denser and more uniform hydrophobic siloxane coating. Analysis of Benzene Sorption Isotherms of Cellulose–Silica Composites The cellulose–silica composites synthesized via the sol–gel method exhibit pronounced hydrophobic characteristics and significantly improved water-repellent properties, making them promising adsorbents for oil and petroleum-based contaminants. Figure 8 presents the adsorption isotherms of MCC, NCC, MCC–(CH₃SiO₁.₅)ₙ, NCC–(CH₃SiO₁.₅)ₙ, and (CH₃SiO₁.₅)ₙ samples. In all cases, adsorption volumes increased gradually with relative pressure (P/P₀ = 0–1), consistent with typical physisorption behavior. Among the tested materials, the MCC– (CH₃SiO₁.₅)ₙ composite exhibited the highest adsorption capacity, reaching 5.3 cm³/g at P/P₀ = 1. The NCC–(CH₃SiO₁.₅)ₙ composite also showed enhanced adsorption performance (maximum 1.8 cm³/g), although lower than MCC–(CH₃SiO₁.₅)ₙ. In contrast, pristine MCC and NCC exhibited significantly lower adsorption volumes (0.88 cm³/g and 0.26 cm³/g, respectively). The pure (CH₃SiO₁.₅)ₙ sample prepared for comparison was synthesized via the sol–gel method using MTMS as precursor. The (CH₃SiO₁.₅)ₙ reference sample displayed moderate capacity (1.4 cm³/g), likely due to surface methylation, which limits the number of accessible adsorption sites. Table 2 Adsorption isotherm parameters of cellulose, silica, and cellulose–silica composites № Indicators MCC MCC-(CH₃SiO₁.₅)ₙ NCC NCC-(CH₃SiO₁.₅)ₙ (CH₃SiO₁.₅)ₙ 1 A m (monolayer capacity), mmol/g 0.26 1.8 0.07 0.6 0,4 2 Specific surface area S, m²/g 61.7 432 15 147 94.4 3 Micropore volume W mic , cm³/g 0.06 0.4 0.02 0.12 0.08 4 Saturation volume V s 0.08 0.5 0.023 0.16 0.12 5 Mesopore volume W mezo , cm³/g 0.02 0,12 0.01 0,04 0.04 6 Pore radius r k , Å 25.3 21.5 31.3 21.5 25.8 The quantitative analysis presented in Table 2 further highlights the structural and adsorption advantages of silica-containing composites. The monolayer capacity (A m ) increased substantially after silica incorporation: from 0.26 → 1.8 mmol/g for MCC and from 0.07 → 0.6 mmol/g for NCC. Similarly, the specific surface area (S) expanded more than sevenfold for MCC– (CH₃SiO₁.₅)ₙ (61.7 → 432 m²/g) and nearly tenfold for NCC – (CH₃SiO₁.₅)ₙ (15 → 147 m²/g). Micropore volume (W mic ) increased significantly (0.06 → 0.4 cm³/g for MCC; 0.02 → 0.12 cm³/g for CNC), indicating the formation of a more developed microporous network. The saturation volume (V s ) also rose sharply, particularly for MCC–(CH₃SiO₁.₅)ₙ (0.5 cm³/g), reflecting higher overall adsorption capacity. Additionally, mesopore volumes doubled or tripled in the composites, highlighting the synergistic contribution of mesoporosity to sorption efficiency. Interestingly, a decrease in average pore radius was observed after silica modification (MCC: 25.3 Å → MCC–(CH₃SiO₁.₅)ₙ: 21.5 Å), suggesting the creation of smaller, more reactive pores, which improve adsorption kinetics. While pure (CH₃SiO₁.₅)ₙ did not exhibit the highest sorption, its balanced microporous and mesoporous structure confirms its utility as a supportive adsorbent. Overall, the results clearly demonstrate that silica incorporation into cellulose significantly enhances specific surface area, microporosity, and sorption efficiency. MCC–(CH₃SiO₁.₅)ₙ composites showed the highest performance, making them strong candidates for practical adsorbent applications. Evaluation of hydrophobic and oleophilic properties. The hydrophobic and oleophilic properties of cellulose–silica composites were evaluated using droplet tests Fig. 9 . The results clearly demonstrate that the composites simultaneously exhibit water-repellent and oil-attracting characteristics, which are crucial for their application as selective adsorbents. When a water droplet was placed on the composite surface, it formed a contact angle greater than 130°, indicating strong hydrophobicity due to the low surface energy and the micro/nanostructured morphology of the material. Conversely, oil droplets spread and were rapidly absorbed into the composite, confirming its pronounced oleophilic behavior. Furthermore, in biphasic water–oil systems, the cellulose–silica composites selectively absorbed the oil phase while leaving the water phase unaffected. This pronounced selectivity confirms their strong potential for applications in oil spill remediation and oily wastewater treatment. Overall, the results highlight the unique dual functionality of cellulose–silica composites, which simultaneously exhibit hydrophobicity (water repellency) and oleophilicity (oil affinity). This combination makes them highly suitable for environmental remediation technologies, including oil spill clean-up, separation of organic pollutants from water, and the purification of industrial effluents. Conclusion In this study, hydrophobic cellulose–silica hybrid composites were successfully synthesized via a sustainable sol–gel approach using microcrystalline (MCC) and nanocrystalline cellulose (NCC) derived from industrial licorice root waste as renewable biopolymer precursors. Methyltrimethoxysilane (MTMS) served both as a silica source and as an in situ hydrophobic modifier, enabling the formation of organically modified siloxane networks directly within the cellulose matrix. FTIR analysis confirmed the formation of Si–O–Si and Si–O–C linkages, indicating effective chemical integration of silica into the cellulose structure, while the retention of –CH₃ groups from MTMS provided reduced surface polarity and enhanced hydrophobicity. XRD results demonstrated a significant decrease in crystallinity (from 69% to 28% for MCC and from 78% to 32% for NCC), reflecting partial disruption of ordered cellulose domains due to silica incorporation and hybrid network formation. Thermogravimetric analysis revealed improved thermal stability of the composites, with degradation temperatures shifting toward higher values compared to pristine cellulose, confirming strong interfacial interactions between the organic and inorganic phases. The hydrophobic performance of the composites was strongly dependent on synthesis parameters. Under optimized conditions (cellulose-to-MTMS molar ratio 1:1.8, 80–100°C, 30–60 min), the water contact angle reached 120° ± 1° for MCC-based composites and 136° ± 1° for NCC-based composites, indicating highly stable hydrophobic surfaces. Time-dependent contact angle measurements further confirmed the durability of the hydrophobic modification, particularly for NCC–(CH₃SiO₁.₅)ₙ composites. Benzene adsorption studies demonstrated a substantial enhancement in adsorption capacity after silica incorporation. The specific surface area increased from 61.7 to 432 m²/g for MCC-based composites and from 15 to 147 m²/g for NCC-based composites, accompanied by a significant increase in micropore volume and monolayer adsorption capacity. Among the investigated samples, MCC–(CH₃SiO₁.₅)ₙ exhibited the highest adsorption performance (5.3 cm³/g at P/P₀ = 1), highlighting the synergistic effect of microstructure and silica-induced porosity. The obtained cellulose–silica composites combine improved thermal stability, high hydrophobicity, developed porous structure, and strong oleophilic behavior, enabling selective oil adsorption from water–oil systems. The use of biomass-derived cellulose from industrial waste further enhances the sustainability and environmental relevance of the developed materials. Overall, this work demonstrates that sol–gel hybridization with MTMS provides an efficient strategy for transforming hydrophilic cellulose into high-performance hydrophobic eco-sorbents. The developed materials show strong potential for applications in oil spill remediation, oily wastewater treatment, and environmentally friendly separation technologies. Declarations Acknowledgment This study was supported by the Fundamental Program of the Academy of Sciences of the Republic of Uzbekistan Author Contributions Аtakhanov A. Abdumutallib: Writing - Original Draft, Conceptualization; Ergashev J. Doniyor: Writing - Original Draft, Formal analysis, Investigation, Methodology; Turdikulov Kh. Islom: Writing - Review & Editing; Yunusov E. Khaydar : Writing - Review & Editing Original Draft; Guohua Jiang: Writing - Review & Editing; Xiaomin Zhu: Writing - Review & Editing . Funding This research was funded by the Ministry of Higher Education, Science and Innovation of the Republic of Uzbekistan under grant number AL-742210856. Data Availability All data that support the findings of this study are included within the article (and any supplementary files). Ethics approval and consent to participate Not applicable. Consent for publication Not applicable. Conflict of Interest The authors declare that there is no conflict of interests regarding the publication of this article. ORCID Аtakhanov Abdumutallib Abdupatto ugli: https://orcid.org/0000-0002-4975-3658 Ergashev Doniyor Jabborovich: https://orcid.org/0000-0003-4547-9142 Turdikulov Islom Hayitboy o’g’li: https://orcid.org/0000-0001-5100-7729 Yunusov Khaydar Ergashovich: https://orcid.org/0000-0002-4646-7859 Guohua Jiang: https://orcid.org/0000-0003-3666-8216 Xiaomin Zhu: https://orcid.org/0000-0002-3887-6791 References Wu W, Yang Y, Zhang J, Lu J (2018) Study on striking ship with loading impact on the performance of the double hull oil tanker collision. Pol Maritime Res. https://doi.org/10.2478/pomr-2018-0072 Nguyen XP, Nguyen DT, Pham VV, Vo DT (2022) Highlights of oil treatment technologies and rise of oil-absorbing materials in ocean cleaning strategy. Water Conserv Manag. https://doi.org/10.26480/wcm.01.2022.06.14 Lang D, Zhang C, Qian Q, Guo C, Wang L, Yang C et al (2023) Oil absorption stability of modified cellulose porous materials with super compressive strength in the complex environment. Cellulose. https://doi.org/10.1007/s10570-023-05322-5 Wang X, Li X Preparation of superhydrophobic membranes with ultraviolet-absorbing capacity for oil–water separation by electrospinning. Polym Eng Sci. https://doi.org/10.1002/pen.26670 Bilal M, Shafiqur MR, Chunbao CX, Tingheng Z, Qin W (2024) Environmental impact associated with oil and grease and their emerging mitigation strategies. J Clean Prod. https://doi.org/10.1007/s12649-024-02425-3 Liew YX, Chan YJ, Manickam S, Chong MF, Chong S, Tiong TJ, Lim JW, Pan GT (2020) Enzymatic pretreatment to enhance anaerobic bioconversion of high strength wastewater to biogas: A review. Sci Total Environ. https://doi.org/10.1016/j.scitotenv.2019.136373 Zhang G, Zhan Y, He S, Zhang L, Zeng G, Chiao YH (2020) Construction of superhydrophilic/underwater superoleophobic polydopamine-modified h-BN/poly(arylene ether nitrile) composite membrane for stable oil-water emulsions separation. Polym Adv Technol. https://doi.org/10.1002/pat.4835 Zhao YH, Guo JX, Zhang XN, An AK, Wang ZK (2022) Superhydrophobic and superoleophilic pH-CNT membrane for emulsified oil-water separation. Desalination. https://doi.org/10.1016/j.desal.2022.115536 Wang H, Guo X, Pei C, Dong W, Yao Y (2022) Hydrophilic modification of polypropylene membrane via tannic and titanium complexation for high efficiency oil/water emulsion separation driven by self gravity. Polym Eng Sci. https://doi.org/10.1002/pen.25994 Woo S, Park HR, Yi Park J, Hwang JW (2020) Robust and continuous oil/water separation with superhydrophobic glass microfiber membrane by vertical polymerization under harsh conditions. Sci Rep. https://doi.org/10.1038/s41598-020-78440-3 Dmitrieva ES, Anokhina TS, Novitsky EG, Volkov VV, Borisov IL, Volkov AV (2022) Polymeric membranes for oil-water separation: A review. Polymers. https://doi.org/10.3390/polym14050980 Guo YQ, Xu C, Liu GL, Xiao K, Zhao HZ (2021) Interpenetrating network nanoarchitectonics of antifouling poly(vinylidene fluoride) membranes for oil-water separation. RSC Adv. https://doi.org/10.1039/D1RA05450H Xu QJ, Tian XL, Jin XG, Wu LL (2021) Inner surface hydrophilic modification of PVDF membrane with tea polyphenols/silica composite coating. Polymers. https://doi.org/10.3390/polym13234186 Olabintan AB, Ahmed EA, Abdulgader H, Saleh TA (2022) Hydrophobic and oleophilic amine-functionalised graphene/polyethylene nanocomposite for oil-water separation. Environ Technol Innov. https://doi.org/10.1016/j.eti.2022.102391 Zhang T, Li Z, Lü Y, Liu Y, Yang D, Li Q, Qiu F (2019) Recent progress and future prospects of oil-absorbing materials. Chin J Chem Eng. https://doi.org/10.1016/j.cjche.2018.09.001 Lin YM, Song C, Rutledge GC (2019) Functionalization of electrospun membranes with polyelectrolytes for separation of oil-in-water emulsions. Adv Mater Interfaces 6(20):1901285. https://doi.org/10.1002/admi.201901285 Khajehamidi M, Gharehaghaji AA, Harifi T (2026) Hydrophobic breathable electrospun nanofibrous PU membranes: An insight into the effect of Si nanoparticles and NaCl. J Polym Res. https://doi.org/10.1007/s10965-025-04725-1 Bhagyaraj S, Sobolciak P, Al-Ghouti MA, Krupa I (2021) Copolyamide-clay nanotube polymer composite nanofiber membranes: preparation, characterization and its asymmetric wettability driven oil/water emulsion separation towards sewage remediation. Polymers. https://doi.org/10.3390/polym13213710 Suzuki R (2024) Effect of adding bentonite to porous silica via the sol–gel method. ACS Omega. https://doi.org/10.1021/acsomega.3c08832 Barud HS, Assuncao RM, Martines MA, Dexpert-Ghys J, Marques RFC, Messaddeq Y, Ribeiro SJL (2008) Bacterial cellulose–silica organic–inorganic hybrids. J Solgel Sci Technol. https://doi.org/10.1007/s10971-007-1669-9 Sonia S, Dmitry VE, Ines P, Ana EP (2007) Synthesis and characterization of cellulose/silica hybrids obtained by heteropoly acid catalysed sol–gel process. Mater Sci Eng C. https://doi.org/10.1016/j.msec.2006.04.007 Hammouda SB et al (2021) Recent advances in developing cellulosic sorbent materials for oil spill cleanup: A state-of-the-art review. J Clean Prod. https://doi.org/10.1016/j.jclepro.2021.127630 Yuldoshov SA, Yunusov KE, Sarymsakov AA, Goyibnazarov IS (2022) Synthesis and characterization of sodium carboxymethylcellulose from cotton, powder, microcrystalline and nanocellulose. Polym Eng Sci. https://doi.org/10.1002/pen.25874 Atakhanov AA, Kholmuminov AA, Mamadiyorov BN, Turdikulov IK, Ashurov NS (2020) Rheological behavior of nanocellulose aqueous suspensions. Polym Sci Ser A. https://doi.org/10.1134/S0965545X20030013 Aggarwal P, Maji S, Purwar R (2026) Structure–property relationships in high-density flexible polyurethane foams reinforced with cellulose nanocrystals (CNC): Comparative effects of particle size. J Polym Res. https://doi.org/10.1007/s10965-026-03137-5 Atakhanov AA, Mamadiyorov B, Kuzieva M, Yugai SM, Shakhobutdinov S, Ashurov NS (2019) Comparative studies of the physicochemical properties and structure of cotton cellulose and its modified forms. Chem Plant Raw Mater. https://doi.org/10.14258/jcprm.2019034554 Mamadiyorov BN, Ergashev DJ, Saidmukhammadova MQ, Ashurov NS, Atakhanov AA (2022) Preparation of micro- and nanocrystalline cellulose from straw cellulose and investigation of its properties. Sci J Sci Innovative Dev. https://doi.org/10.36522/2181-9637-2022-4-1 Kuzieva MA, Atakhanov AA, S, hakhobutdinov SS, Ashurov NS, Yunusov KE, Guohua J (2023) Preparation of oxidized nanocellulose by using potassium dichromate. Cellulose. https://doi.org/10.1007/s10570-023-05222-8 Morais JPS, Rosa MF, Filho MMS, Nascimento LD, Nascimento DM, Cassales AR (2013) Extraction and characterization of nanocellulose structures from raw cotton linter. Carbohydr Polym. https://doi.org/10.1016/j.carbpol.2012.08.010 Suhas VK, Gupta PJ, Carrott M, Chaudhary M, Kushwaha S (2016) Cellulose: a review as natural, modified and activated carbon adsorbent. Bioresour Technol. https://doi.org/10.1016/j.biortech.2016.05.106 An Y et al (2024) Hydrophobic modification of cellulose acetate and its application in the field of water treatment: A review. Molecules. https://doi.org/10.3390/molecules29215127 Chen L et al (2018) Water adsorption on hydrophilic and hydrophobic surfaces of silicon. J Phys Chem C. https://doi.org/10.1021/acs.jpcc.8b01821 Jia W, Tian J, Liu W, Niu J, Zhang J, Junchao L, Li J, Yu X, Gao H (2025) Research progress and applications of cellulose-based functional materials. Polym Adv Technol. https://doi.org/10.1002/pat.70318 Darmakkolla SR et al (2016) A method to derivatize surface silanol groups to Si-alkyl groups in carbon-doped silicon oxides. RSC Adv. https://doi.org/10.1039/C6RA20355H Luo T et al (2021) Hydrophobic modification of silica surfaces via grafting alkoxy groups. ACS Appl Electron Mater. https://doi.org/10.1021/acsaelm.1c00017 Pinto RB, Marques PA, Barros-Timmons AM, Trindade T, Neto CP (2008) Novel SiO₂/cellulose nanocomposites obtained by in situ synthesis and via polyelectrolytes assembly. Compos Sci Technol. https://doi.org/10.1016/j.compscitech.2007.03.001 Hribernik S, Smole MS, Kleinschek KS, Bele M, Jamnik J, Gaberscek M (2007) Flame retardant activity of SiO₂-coated regenerated cellulose fibres. Polym Degrad Stab. https://doi.org/10.1016/j.polymdegradstab.2007.08.010 Rosaria C, Alexandra F, Valerica P, François BL, Laura MI, Mario P (2013) The sol–gel route to advanced silica-based materials and recent applications. Chem Rev. https://doi.org/10.1021/cr300399c Lavorgna M, Verdolotti L, Mascia L (2015) Organic–inorganic bio-hybrid materials by sol–gel processing. Biofoams: Science and Applications of Bio-Based Cellular and Porous Materials. https://doi.org/10.1039/D1CS00519G Shange MG et al (2024) Factors affecting silica/cellulose nanocomposite prepared via the sol–gel technique: A review. Materials. https://doi.org/10.3390/ma17091937 Hussain A, Calabria-Holley J, Schorr D, Jiang Y, Lawrence BP (2018) Hydrophobicity of hemp shiv treated with sol–gel coatings. Appl Surf Sci. https://doi.org/10.1016/j.apsusc.2017.10.210 Tan B, Rankin SE (2006) Study of the effects of progressive changes in alkoxysilane structure on sol–gel reactivity. J Phys Chem B. https://doi.org/10.1021/jp060376k Chrusciel JJ, Lesniak E (2015) Modification of epoxy resins with functional silanes, polysiloxanes, silsesquioxanes, silica and silicates. Prog Polym Sci. https://doi.org/10.1016/j.progpolymsci.2014.08.001 Vasquez A, Cyras VP, Alvarez VA, Moran JI (2012) Starch/clay nano-biocomposites. In: Averous L, Pollet E (eds) Environmental Silicate Nano-Biocomposites. Springer, London, UK. https://doi.org/10.1155/2015/493439 Shakhabutdinov SS, Yugay SM, Ashurov NS, Ergashev DJ, Atakhanov AA, Rashidova SS (2024) Characterization of electrospun nanofibers based on cellulose triacetate synthesized from licorice root cellulose. Eurasian J Chem. https://doi.org/10.31489/2959-0663/2-24-2 Kyung-Soo K, Jun-Kyung K, Woo-Sik K (2002) Influence of reaction conditions on sol-precipitation process producing silicon oxide particles. Ceram Int. https://doi.org/10.1016/S0272-8842(01)00076-1 Masoud M, Malihe BZ, Mahdieh D, Khalilollah S, Seyed TK, Jalil S, Azadeh F, Hajar M (2020) Silica mesoporous structures: Effective nanocarriers in drug delivery and nanocatalysts. Appl Sci. https://doi.org/10.3390/app10217533 Joabel R, Alessandra SF, Lina B, Caue R, Maria AM, Jose MM, Gustavo H, Denzin T (2014) Evaluation of reaction factors for deposition of silica (SiO₂) nanoparticles on cellulose fibers. Carbohydr Polym. https://doi.org/10.1016/j.carbpol.2014.08.042 Musawenkosi GS, Nduduzo LK, Samson MM, Tshwafo EM (2024) Factors affecting silica/cellulose nanocomposite prepared via the sol–gel technique: A review. Materials. https://doi.org/10.3390/ma17091937 Lu J, Shi J, Guo LW, Zhang J, Cao Y (2013) Heat insulation performance, mechanics and hydrophobic modification of cellulose–SiO₂ composite aerogels. Carbohydr Polym. https://doi.org/10.1016/j.carbpol.2013.05.082 Ning J, Shu-Ming S, Ming-Guo M, Jie-Fang J, Run-Cang S (2011) Synthesis of cellulose silica composite. BioResources. https://doi.org/10.15376/biores.6.2.1186-1195 Fan S, Kunthom R, Meng Y, Kostjuk SV, Liu H (2025) Superhydrophobic fabric coated with double-decker silsesquioxane-based hybrid polymer for efficient oil/water separation and enhanced antifouling performance. Cellulose. https://doi.org/10.1007/s10570-025-05585-6 Cite Share Download PDF Status: Under Review Version 1 posted Reviewers agreed at journal 03 Apr, 2026 Reviewers invited by journal 03 Apr, 2026 Editor invited by journal 02 Apr, 2026 Editor assigned by journal 30 Mar, 2026 First submitted to journal 27 Mar, 2026 You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-9245876","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":617045014,"identity":"5d29d902-929e-4417-b85a-9e224730812c","order_by":0,"name":"Doniyor Jabborovich 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14:33:11","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-9245876/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-9245876/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":106533446,"identity":"bcbb4a3c-d65a-47eb-91a3-467714961786","added_by":"auto","created_at":"2026-04-09 14:57:27","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":525554,"visible":true,"origin":"","legend":"\u003cp\u003eFTIR spectra of MCC, NCC, (CH₃SiO₁.₅)ₙ\u003cem\u003e, \u003c/em\u003eand CSC samples\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-9245876/v1/d0cf1b049714fb6358a46af9.png"},{"id":106724673,"identity":"50575a69-2308-4f65-bde4-5b04a9cf22d0","added_by":"auto","created_at":"2026-04-12 18:29:05","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":397313,"visible":true,"origin":"","legend":"\u003cp\u003eX-ray diffraction patterns of NCC, MCC, (CH₃SiO₁.₅)ₙ,\u003cem\u003e \u003c/em\u003eand CSC samples\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-9245876/v1/eec74d23ea7471b2f1663e42.png"},{"id":106533456,"identity":"91be5d20-bab9-42d9-822d-7178e56da478","added_by":"auto","created_at":"2026-04-09 14:57:30","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":261733,"visible":true,"origin":"","legend":"\u003cp\u003eThermogravimetric (TG) curves of the samples\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-9245876/v1/d12a4a4e3480008433e5b1b2.png"},{"id":106533532,"identity":"c7901a49-cfbc-4340-a352-ddf6f36e5579","added_by":"auto","created_at":"2026-04-09 14:57:41","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":216219,"visible":true,"origin":"","legend":"\u003cp\u003eWater contact angle values of MCC- and NCC-based composites as a function of the cellulose/MTMS molar ratio\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-9245876/v1/1b2e41b40e2410dbefc95653.png"},{"id":106533444,"identity":"4434827d-fd68-49fe-b5cc-b864d4445069","added_by":"auto","created_at":"2026-04-09 14:57:27","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":218155,"visible":true,"origin":"","legend":"\u003cp\u003eRelationship between reaction temperature and water contact angle for MCC–(CH₃SiO₁.₅)ₙ and NCC –(CH₃SiO₁.₅)ₙ composites (cellulose-to-MTMS ratio of 1:1.8)\u003c/p\u003e","description":"","filename":"5.png","url":"https://assets-eu.researchsquare.com/files/rs-9245876/v1/ce83a07825f0feef13f94ba6.png"},{"id":106533573,"identity":"acb40869-a6c0-4dd1-bcae-4cfe10f0d3f0","added_by":"auto","created_at":"2026-04-09 14:57:47","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":148800,"visible":true,"origin":"","legend":"\u003cp\u003eRelationship between reaction time and water contact angle for MCC–(CH₃SiO₁.₅)ₙ and NCC–(CH₃SiO₁.₅)ₙ composites (cellulose-to-MTMS ratio of 1:1.8 and temperature range of 80–100 °C)\u003c/p\u003e","description":"","filename":"6.png","url":"https://assets-eu.researchsquare.com/files/rs-9245876/v1/8f565adb474bd5d8bb9349d0.png"},{"id":106533578,"identity":"058ed71e-8eca-40e8-ad3c-2c6c2c8bb119","added_by":"auto","created_at":"2026-04-09 14:57:47","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":263940,"visible":true,"origin":"","legend":"\u003cp\u003eTime-dependent changes in water contact angle for \u003cem\u003e\u003cstrong\u003e(a)\u003c/strong\u003e\u003c/em\u003e\u003cem\u003e MCC \u003c/em\u003e\u003cem\u003e\u003cstrong\u003e(b) \u003c/strong\u003e\u003c/em\u003e\u003cem\u003eMCC–(CH₃SiO₁.₅)ₙ \u003c/em\u003e\u003cem\u003e\u003cstrong\u003e(c) \u003c/strong\u003e\u003c/em\u003e\u003cem\u003eNCC and \u003c/em\u003e\u003cem\u003e\u003cstrong\u003e(d) \u003c/strong\u003e\u003c/em\u003e\u003cem\u003eNCC –(CH₃SiO₁.₅)ₙ\u003c/em\u003e\u003c/p\u003e","description":"","filename":"7.png","url":"https://assets-eu.researchsquare.com/files/rs-9245876/v1/5010435bb3f95f9ee18f949d.png"},{"id":106533508,"identity":"b70e9133-24f8-469b-a4f9-010bbbe654ce","added_by":"auto","created_at":"2026-04-09 14:57:34","extension":"png","order_by":8,"title":"Figure 8","display":"","copyAsset":false,"role":"figure","size":222431,"visible":true,"origin":"","legend":"\u003cp\u003eSorption isotherms of the samples based on adsorption volume under increasing relative pressure\u003c/p\u003e","description":"","filename":"8.png","url":"https://assets-eu.researchsquare.com/files/rs-9245876/v1/38949abfbb7d61047efd0ce8.png"},{"id":106533582,"identity":"ced23beb-c459-46f2-9b7e-8232dbc99455","added_by":"auto","created_at":"2026-04-09 14:57:47","extension":"png","order_by":9,"title":"Figure 9","display":"","copyAsset":false,"role":"figure","size":1045373,"visible":true,"origin":"","legend":"\u003cp\u003eEvaluation of hydrophobic and oleophilic properties of CSC:\u003cem\u003e (\u003c/em\u003e\u003cem\u003e\u003cstrong\u003ea)\u003c/strong\u003e\u003c/em\u003e\u003cem\u003e Contact angle tests with water and oil droplets placed on the CSC surface: the water droplet remains spherical (hydrophobicity), whereas the oil droplet is rapidly absorbed (oleophilicity); (\u003c/em\u003e\u003cem\u003e\u003cstrong\u003eb)\u003c/strong\u003e\u003c/em\u003e\u003cem\u003e Selective absorption of oil versus water when the CSC is placed at the interface of separated liquids. The composite strongly absorbs oil while repelling water; (\u003c/em\u003e\u003cem\u003e\u003cstrong\u003ec)\u003c/strong\u003e\u003c/em\u003e\u003cem\u003e Separation experiments in water–oil mixtures: the CSC selectively removes oil from the mixture, leaving the water phase clear.\u003c/em\u003e\u003c/p\u003e","description":"","filename":"9.png","url":"https://assets-eu.researchsquare.com/files/rs-9245876/v1/d133d52c3ba667057cc37d5b.png"},{"id":106726582,"identity":"672f2c64-b9f8-4e60-ba41-20489ef8b078","added_by":"auto","created_at":"2026-04-12 18:36:38","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":4880386,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-9245876/v1/8f9c6272-6dbe-4ee0-b823-58bee9ff0cd2.pdf"}],"financialInterests":"","formattedTitle":"Micro- and nanocellulose-based silica hybrid nanocomposites as eco-sorbents for efficient oil removal","fulltext":[{"header":"Introduction","content":"\u003cp\u003eThe drive to consume more energy is leading to a sharp increase in oil-contaminated wastewater Failures in transportation and processing systems\u0026mdash;and disasters at sea involving tankers\u0026mdash;have led to catastrophic pollution. This contamination hits marine ecosystems hardest and may cause long-term damage, including the loss of vulnerable species. [\u003cspan additionalcitationids=\"CR2 CR3\" citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e]. Environmental protection from oil and grease contamination represents one of the most pressing ecological challenges. Hydrocarbon pollution of marine waters, particularly by oil and grease, has become a serious global concern [\u003cspan additionalcitationids=\"CR6 CR7 CR8\" citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e]. Among the available technologies for oily wastewater treatment, membrane separation has attracted increasing attention due to its simplicity, energy efficiency, environmental safety, high separation performance, and cost-effectiveness [\u003cspan additionalcitationids=\"CR11 CR12 CR13\" citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e]. It is widely recognized that oily effluents carry organics of intricate composition, elevated biotoxicity, and low biodegradability [\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eHydrophobic and oleophilic materials play a pivotal role in tackling this issue, especially when derived from natural and renewable resources, as they are both eco-friendly and effective [\u003cspan additionalcitationids=\"CR17\" citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e]. Among potential precursors for sorbent synthesis, cellulose derivatives and silica compounds stand out as highly promising candidates, particularly when combined through sol\u0026ndash;gel synthesis [\u003cspan additionalcitationids=\"CR20 CR21\" citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eCellulose, the most abundant and renewable natural polymer, has gained remarkable attention in its modified forms such as microcrystalline cellulose (MCC) and nanocrystalline cellulose (NCC) [\u003cspan additionalcitationids=\"CR24 CR25 CR26 CR27\" citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e]. As a key structural component of plants, cellulose exhibits high absorbency, mechanical strength, and biodegradability, which make it suitable for different applications [\u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e, \u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e]. However, the inherent hydrophilicity of native cellulose restricts its ability to remove hydrophobic contaminants such as oil and grease from aqueous media, highlighting the necessity of hydrophobic modification [\u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e31\u003c/span\u003e, \u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eSilica-based compounds, in turn, are well known for their thermal stability as well as unique optical, electronic, and mechanical properties, which underpin their wide range of applications [\u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e]. The silica surface is rich in silanol groups (Si\u0026ndash;OH), which are hydrophilic yet chemically reactive, allowing for hydrophobic functionalization [\u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e, \u003cspan citationid=\"CR35\" class=\"CitationRef\"\u003e35\u003c/span\u003e]. Through covalent bonding with organic molecules, silica can be converted into organic\u0026ndash;inorganic hybrid materials with applications in sensors, catalysts, adsorbents, and biomaterials [\u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e36\u003c/span\u003e, \u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e37\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eCellulose\u0026ndash;silica composites can be synthesized by three main approaches: the sol\u0026ndash;gel method, layer-by-layer assembly, and biomineralization-inspired techniques [\u003cspan additionalcitationids=\"CR39\" citationid=\"CR38\" class=\"CitationRef\"\u003e38\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR40\" class=\"CitationRef\"\u003e40\u003c/span\u003e]. Among these, the sol\u0026ndash;gel route is the most widely employed, as it enables molecular-level control over material composition and microstructure under mild and low-energy conditions. Typical precursors include methyltrimethoxysilane (MTMS), tetraethoxysilane (TEOS), and tetramethoxysilane (TMOS), which undergo hydrolysis to form reactive silanol groups that condense into a stable silica network (gel). The resulting silica surface, rich in chemically active silanol groups, offers versatile opportunities for further functionalization [\u003cspan additionalcitationids=\"CR42 CR43\" citationid=\"CR41\" class=\"CitationRef\"\u003e41\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR44\" class=\"CitationRef\"\u003e44\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eIn this context, the present study focuses on the development of hydrophobic cellulose\u0026ndash;silica composite materials synthesized via the sol\u0026ndash;gel method. Cellulose obtained from industrial licorice-root waste, an inexpensive raw material, was used as a renewable precursor in its microcrystalline (MCC) and nanocrystalline (NCC) forms. Methyltrimethoxysilane (MTMS) was employed as the silicon source as well as the hydrophobic modifying agent. During condensation, MTMS retains the \u0026ndash;CH₃ group within the resulting silica network. The \u0026ndash;CH₃ functional group is an organic radical characterized by low polarity, low dielectric constant, and strong Van der Waals interactions (similar to hydrocarbons), which converts the structure into an organically modified silica and inherently imparts hydrophobicity. In contrast, silica derived from TEOS/TMOS generally exhibits hydrophilic properties. The objectives of the study were to investigate the influence of key synthesis parameters, including MCC/MTMS molar ratio, reaction temperature, and reaction time, on the formation of cellulose\u0026ndash;silica composites; characterize the morphology, structure, and thermal stability of the obtained materials using XRD, FTIR, and TGA; and evaluate the hydrophobicity and sorption performance of the composites toward oil and grease. The findings are expected to provide valuable insights into the design of eco-friendly, bio-based hybrid sorbents for efficient treatment of oily wastewater and environmental remediation.\u003c/p\u003e"},{"header":"Materials and Methods","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e\n \u003ch2\u003eMaterials\u003c/h2\u003e\n \u003cp\u003eMicrocrystalline cellulose (MCC) with a degree of crystallinity of 69% and a degree of polymerization of 350\u0026ndash;400, and nanocrystalline cellulose (NCC) with a degree of crystallinity of 78% and a degree of polymerization of 150\u0026ndash;250, were derived from licorice root cellulose extracted in our previous study.\u003c/p\u003e\n \u003cp\u003eMethyltrimethoxysilane (MTMS, \u0026ge;\u0026thinsp;98%, CAS No. 1185-55-3), Sulphuric acid (H₂SO₄, CAS No. 7664-93-9), ethanol (C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e5\u003c/sub\u003eOH, \u0026ge;\u0026thinsp;95%, CAS No. 61-73-4), Nitrite acid (HNO₃, CAS No. 7697-37-2), hydrochloric acid (HCl, 0.1 N, CAS No. 7647-01-0), and ammonium hydroxide (NH₄OH, 0.1 N, CAS No. 1336-21-6) were purchased from commercial suppliers (Sigma-Aldrich, China) and used without further purification. Distilled water was used throughout all experiments.\u003c/p\u003e\n\u003c/div\u003e\n\u003ch2\u003eSample Preparation\u003c/h2\u003e\n\u003ch2\u003ePreparation of Nanocrystalline Cellulose (NCC)\u003c/h2\u003e\n\u003cp\u003eNCC was prepared by the previously method [\u003cspan citationid=\"CR45\" class=\"CitationRef\"\u003e45\u003c/span\u003e] using acid hydrolysis of licorice root cellulose in 55% H₂SO₄ at 50\u0026deg;C, maintaining a cellulose-to-acid ratio of 1:10 (w/v). The reaction was conducted for 90 min under constant stirring, followed by dilution with cold water, centrifugation, and repeated washing until neutrality was achieved.\u003c/p\u003e\n\u003ch3\u003ePreparation of Microcrystalline Cellulose (MCC)\u003c/h3\u003e\n\u003cp\u003eMCC was obtained by the previously method [\u003cspan citationid=\"CR45\" class=\"CitationRef\"\u003e45\u003c/span\u003e] from licorice root cellulose by hydrolysis in a 4% HNO₃ solution in an autoclave at 100\u0026ndash;110\u0026deg;C for 60 minutes, using a cellulose-to-acid ratio of 1:10 (w/v). The resulting product was filtered, thoroughly washed with distilled water until a neutral pH was reached, and dried at 100\u0026ndash;105\u0026deg;C.\u003c/p\u003e\n\u003ch3\u003eSynthesis of Cellulose\u0026ndash;Silica Composites (CSC)\u003c/h3\u003e\n\u003cp\u003eCellulose suspensions were prepared by dispersing 1.05 g of either MCC or NCC in 10 mL of ethanol, followed by homogenization using an IKA Ultra-Turrax Tube Disperser (Germany) at 5000 rpm for 1 h.\u003c/p\u003e\n\u003cp\u003eFor the hydrolysis of MTMS, 2 mL of MTMS was mixed with 2 mL of ethanol (95%) and 1 mL of HCl (0.1 N) at room temperature. The mixture was stirred at 500 rpm for 1 h to generate reactive silanol groups.\u003c/p\u003e\n\u003cp\u003eIn the subsequent step, the cellulose suspension was added dropwise to the hydrolyzed MTMS solution under continuous stirring. After 10 min, 1 mL of 0.1 N NH₄OH was added to initiate the gelation process, and the mixture was further stirred at 500 rpm for an additional 1 h. The resulting gel was washed several times with distilled water and ethanol, and then dried at 100\u0026ndash;105\u0026deg;C.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eFor comparison with the composite materials, pure methyl silicate salt was synthesized.\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eFor the hydrolysis of MTMS, 2 mL of MTMS was mixed with 2 mL of 95% ethanol and 1 mL of 0.1 N HCl at room temperature. The resulting mixture was stirred at 500 rpm for 1 h to generate reactive silanol groups. Subsequently, to initiate the condensation process, 1 mL of 0.1 N NH₄OH was added to the hydrolyzed MTMS solution, and the mixture was further stirred at 500 rpm for an additional 1 h. The resulting gel was washed several times with distilled water and ethanol, and then dried at 100\u0026ndash;105\u0026deg;C.\u003c/p\u003e\n\u003cdiv id=\"Sec8\" class=\"Section2\"\u003e\n \u003ch2\u003eCharacterization\u003c/h2\u003e\n \u003cdiv id=\"Sec9\" class=\"Section3\"\u003e\n \u003ch2\u003eFourier-transform infrared spectroscopy (FTIR)\u003c/h2\u003e\n \u003cp\u003eSpectra were recorded on a Bruker Inventio-S IR spectrometer (Germany) in the range 500\u0026ndash;4000 cm⁻\u0026sup1;.\u003c/p\u003e\n \u003c/div\u003e\n\u003c/div\u003e\n\u003ch2\u003eX-ray diffraction (XRD)\u003c/h2\u003e\n\u003cp\u003eAnalysis was performed using a Rigaku Miniflex 600 diffractometer (Japan) with monochromatic CuK\u0026alpha; radiation (\u0026lambda;\u0026thinsp;=\u0026thinsp;1.5418 \u0026Aring;, Ni filter). Operating conditions: 40 kV, 15 mA; scan range: 2\u0026theta;\u0026thinsp;=\u0026thinsp;5\u0026ndash;40\u0026deg;. Data analysis involved peak deconvolution, Miller indexing, and amorphous content quantification using SmartLab Studio II and the ICDD PDF-2 (2020) database.\u003c/p\u003e\n\u003cdiv id=\"Sec11\" class=\"Section2\"\u003e\n \u003ch2\u003eThermogravimetric analysis (TGA)\u003c/h2\u003e\n \u003cp\u003eConducted with a Linseis STA TG-DTA/DSC \u0026ldquo;Start-1600\u0026rdquo; system (Germany) under air atmosphere, heating rate 10\u0026deg;C/min, within the range 20\u0026ndash;800\u0026deg;C.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec12\" class=\"Section2\"\u003e\n \u003ch2\u003eWater contact angle (WCA)\u003c/h2\u003e\n \u003cp\u003eThe hydrophobicity of the composites was evaluated by static water contact angle measurements using a Drop Shape Analyzer \u0026ndash; DSA25 (KR\u0026Uuml;SS GmbH, Germany) A 5 \u0026micro;L deionized water droplet was placed on the composite surface, and images were captured after 10 s. Reported values represent the average of at least five independent measurements. The technical specifications of the DSA25 indicate that the sessile (static) droplet method allows measurements in the range of 0\u0026deg;\u0026ndash;180\u0026deg;. The reported accuracy is given as approximately 0.1\u0026deg; to 1\u0026deg;.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec13\" class=\"Section2\"\u003e\n \u003ch2\u003eBenzene sorption isotherm studies\u003c/h2\u003e\n \u003cp\u003eThe benzene vapor adsorption capacity of the samples was determined using a volumetric adsorption analyzer, Autosorb iQ (Anton Paar, Austria). Prior to analysis, the samples (\u0026asymp;\u0026thinsp;100 mg) were degassed under vacuum at 60\u0026deg;C for 12 h to remove physically adsorbed moisture. Adsorption isotherms were recorded at 25\u0026deg;C over a relative pressure (P/P₀) range of 0.05\u0026ndash;0.95. The equilibrium sorption capacity was calculated based on the amount of adsorbed benzene vapor per unit mass of the dried sample.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec14\" class=\"Section2\"\u003e\n \u003ch2\u003eStatistical analysis\u003c/h2\u003e\n \u003cp\u003eAll experimental data were collected in triplicates and data expressed as the mean\u0026thinsp;\u0026plusmn;\u0026thinsp;standard deviation. Data were compared using a one-way ANOVA with post-Bonferroni test using GraphPad Prism 5.04 (GraphPad Software Inc., San Diego, California), with p\u0026thinsp;\u0026lt;\u0026thinsp;0.05 depicting significant difference between data sets\u003c/p\u003e\n\u003c/div\u003e"},{"header":"Results and Discussion","content":"\u003cdiv id=\"Sec16\" class=\"Section2\"\u003e\n \u003ch2\u003eFTIR Spectroscopy Analysis\u003c/h2\u003e\n \u003cp\u003eThe FTIR spectra of pristine microcrystalline cellulose (MCC) and nanocrystalline cellulose (NCC) (curves 1 and 2) exhibit characteristic absorption bands typical of cellulose.\u003c/p\u003e\n \u003cp\u003eThe broad band observed in the range of 3350\u0026ndash;3450 cm⁻\u0026sup1; is attributed to the stretching vibrations of hydroxyl (\u0026ndash;OH) groups, indicating the presence of strong intermolecular and intramolecular hydrogen bonding within the cellulose structure. The absorption bands around 2900 cm⁻\u0026sup1; correspond to the C\u0026ndash;H stretching vibrations of aliphatic \u0026ndash;CH and \u0026ndash;CH₂ groups. The band located near 1640 cm⁻\u0026sup1; is associated with the bending vibrations of adsorbed water molecules. In addition, the bands in the 1000\u0026ndash;1150 cm⁻\u0026sup1; region are assigned to the stretching vibrations of C\u0026ndash;O\u0026ndash;C and C\u0026ndash;O bonds of the pyranose ring, confirming the polysaccharide backbone of cellulose. The FTIR spectrum of pristine metilsiloksan ((CH₃SiO₁.₅)ₙ) displays well-defined absorption bands in the range of 1080\u0026ndash;1100 cm⁻\u0026sup1;, which are mainly attributed to the asymmetric stretching vibrations of Si\u0026ndash;O\u0026ndash;Si bonds within the siloxane network. The band observed around 800 cm⁻\u0026sup1; corresponds to the symmetric stretching vibrations of Si\u0026ndash;O\u0026ndash;Si bonds, while the absorption near 460 cm⁻\u0026sup1; is associated with the bending vibrations of the siloxane framework [\u003cspan additionalcitationids=\"CR47\" citationid=\"CR46\" class=\"CitationRef\"\u003e46\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR48\" class=\"CitationRef\"\u003e48\u003c/span\u003e]. Furthermore, the presence of absorption bands in the range of 1270\u0026ndash;1260 cm⁻\u0026sup1; is assigned to the stretching vibrations of Si\u0026ndash;CH₃ bonds, indicating the retention of methyl groups within the siloxane network. The bands observed in the 2970\u0026ndash;2850 cm⁻\u0026sup1; region are attributed to the C\u0026ndash;H stretching vibrations of methyl groups. These spectral features confirm that the methyl silicate salt possesses an organically modified siloxane structure, accounting for its low polarity and inherent hydrophobic characteristics. The FTIR spectra of the MCC\u0026ndash;(CH₃SiO₁.₅)ₙ and NCC\u0026ndash;(CH₃SiO₁.₅)ₙ composites (curves 3 and 4) exhibit combined features characteristic of both cellulose and silica, confirming the successful formation of hybrid composites. The reduced intensity of the \u0026ndash;OH stretching band in the 3350\u0026ndash;3450 cm⁻\u0026sup1; region compared to pristine cellulose indicates the occurrence of condensation reactions between the hydroxyl groups of cellulose and the silanol groups generated from MTMS. The appearance and enhancement of absorption bands in the 1000\u0026ndash;1100 cm⁻\u0026sup1; region are attributed to the overlapping stretching vibrations of Si\u0026ndash;O\u0026ndash;Si and Si\u0026ndash;O\u0026ndash;C bonds, providing strong evidence for the formation of covalent linkages between the cellulose matrix and the silica network. Moreover, the presence of absorption bands in the 2970\u0026ndash;2850 cm⁻\u0026sup1; region, along with weak bands observed at 1270\u0026ndash;1260 cm⁻\u0026sup1; in the composite samples, are associated with the stretching vibrations of Si\u0026ndash;CH₃ bonds originating from MTMS, indicating that methyl groups are retained within the silica structure. These organic moieties lead to the formation of organically modified silica and significantly enhance the hydrophobic properties of the composites. Overall, the FTIR analysis clearly demonstrates that silica was successfully integrated into the cellulose structure via the sol\u0026ndash;gel process and that effective surface modification was achieved using MTMS. The formation of Si\u0026ndash;O\u0026ndash;Si and Si\u0026ndash;O\u0026ndash;C bonds, together with the retention of \u0026ndash;CH₃ groups, confirms the development of cellulose\u0026ndash;silica composites with tailored structural and surface properties and markedly enhanced hydrophobicity.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec17\" class=\"Section2\"\u003e\n \u003ch2\u003eXRD Analysis\u003c/h2\u003e\n \u003cp\u003eTo further investigate and compare the amorphous and crystalline structures of cellulose\u0026ndash;silica composites, X-ray diffraction (XRD) analysis was performed Fig. \u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e.\u003c/p\u003e\n \u003cp\u003eThe X-ray diffraction (XRD) patterns of the samples synthesized based on MTMS were investigated in order to evaluate the crystalline structure of cellulose and the structural influence of the methylsiloxane phase. The diffractograms of pure nanocrystalline cellulose (NC, curve 1) and microcrystalline cellulose (MCC, curve 2) exhibited sharp and intense diffraction peaks characteristic of cellulose I. The main diffraction peak located at 2\u0026theta;\u0026thinsp;\u0026asymp;\u0026thinsp;22\u0026ndash;23\u0026deg; corresponds to the (200) crystallographic plane, while additional peaks observed in the 2\u0026theta;\u0026thinsp;\u0026asymp;\u0026thinsp;14\u0026ndash;16\u0026deg; range are attributed to the (1̅10) and (110) planes.\u003c/p\u003e\n \u003cp\u003eBased on crystallinity index calculations, the CrI value of the NC sample was determined to be 78%, whereas that of the MCC sample was 69%, indicating a higher degree of crystallinity for nanocrystalline cellulose.\u003c/p\u003e\n \u003cp\u003eThe diffractogram of pure methylsiloxane ((CH₃SiO₁.₅)ₙ, curve 5) showed no distinct crystalline diffraction peaks; instead, a broad, low-intensity halo centered at 2\u0026theta;\u0026thinsp;\u0026asymp;\u0026thinsp;20\u0026ndash;25\u0026deg; was observed, confirming the amorphous nature of the siloxane network. This result indicates that the methylsiloxane phase derived from MTMS does not form a long-range ordered crystalline structure.\u003c/p\u003e\n \u003cp\u003eIn the diffractograms of the NC\u0026ndash;(CH₃SiO₁.₅)ₙ and MCC\u0026ndash;(CH₃SiO₁.₅)ₙ composites (curves 3 and 4), the main cellulose-related diffraction peaks were preserved; however, their intensities were significantly reduced compared to those of the pristine NC and MCC samples. The crystallinity index decreased sharply to 32% for NC\u0026ndash;(CH₃SiO₁.₅)ₙ and 28% for MCC\u0026ndash;(CH₃SiO₁.₅)ₙ. This pronounced reduction indicates that the incorporation of the methylsiloxane phase into the cellulose matrix disrupts the regular arrangement of cellulose chains and leads to partial destruction of the ordered crystalline domains.\u003c/p\u003e\n \u003cdiv class=\"gridtable\"\u003e\u0026nbsp;\u003ctable float=\"Yes\" id=\"Tab1\" border=\"1\"\u003e\n \u003ccaption language=\"En\"\u003e\n \u003cdiv class=\"CaptionNumber\"\u003eTable 1\u003c/div\u003e\n \u003cdiv class=\"CaptionContent\"\u003e\n \u003cp\u003eCrystallinity index of NCC, MCC, and CSC samples\u003c/p\u003e\n \u003c/div\u003e\n \u003c/caption\u003e\n \u003ccolgroup cols=\"2\"\u003e\u003c/colgroup\u003e\n \u003cthead\u003e\n \u003ctr\u003e\n \u003cth align=\"left\" colname=\"c1\"\u003e\n \u003cp\u003eSample\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\" colname=\"c2\"\u003e\n \u003cp\u003eCrystallinity index (CrI, %)\u003c/p\u003e\n \u003c/th\u003e\n \u003c/tr\u003e\n \u003c/thead\u003e\n \u003ctbody\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" colname=\"c1\"\u003e\n \u003cp\u003eMCC\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e\n \u003cp\u003e69\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" colname=\"c1\"\u003e\n \u003cp\u003eNCC\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e\n \u003cp\u003e78\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" colname=\"c1\"\u003e\n \u003cp\u003eMCC\u0026ndash;(CH₃SiO₁.₅)ₙ\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e\n \u003cp\u003e28\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" colname=\"c1\"\u003e\n \u003cp\u003eNCC\u0026ndash;(CH₃SiO₁.₅)ₙ\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e\n \u003cp\u003e32\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n \u003c/table\u003e\n \u003c/div\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec18\" class=\"Section2\"\u003e\n \u003ch2\u003eThermogravimetric Analysis\u003c/h2\u003e\n \u003cp\u003eFigure \u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e presents the thermogravimetric (TG) curves of MCC, NCC, and their cellulose\u0026ndash;silica composites, illustrating the influence of silica incorporation on thermal stability.\u003c/p\u003e\n \u003cp\u003eThe TGA profiles of all samples reveal a three-step weight-loss behavior. The first stage, observed between 60\u0026ndash;150\u0026deg;C, corresponds to the removal of physically adsorbed moisture. This is a typical feature of cellulose-based materials due to their inherent hydrophilicity.\u003c/p\u003e\n \u003cp\u003eThe second stage corresponds to the principal thermal degradation of cellulose, and its temperature range depends on the sample composition. For pure MCC, degradation occurs within 295\u0026ndash;315\u0026deg;C, while for MCC\u0026ndash;(CH₃SiO₁.₅)ₙ composites this range shifts upward to 305\u0026ndash;345\u0026deg;C. Similarly, pure NCC decomposes at ~\u0026thinsp;300\u0026ndash;330\u0026deg;C, whereas NCC\u0026ndash;(CH₃SiO₁.₅)ₙ composites exhibit delayed degradation between 325\u0026ndash;375\u0026deg;C. This noticeable increase in decomposition temperature indicates a significant enhancement in thermal stability upon hybridization. The improvement can be attributed to strong hydrogen bonding and possible covalent interactions between cellulose hydroxyl groups and silica silanols, which restrict polymer chain mobility and slow down thermal decomposition [\u003cspan citationid=\"CR49\" class=\"CitationRef\"\u003e49\u003c/span\u003e].\u003c/p\u003e\n \u003cp\u003eThe third stage corresponds to complete decomposition of the cellulose fraction, leaving behind a silica-rich residue. The higher char yield observed in CSC compared to pristine cellulose further confirms the successful integration of thermally stable inorganic silica into the organic matrix.\u003c/p\u003e\n \u003cp\u003eOverall, the incorporation of silica substantially improves the thermal stability of cellulose, broadening the operational temperature window of the composites. These results emphasize the potential of cellulose\u0026ndash;silica hybrids for high-temperature applications such as flame-retardant coatings, thermal insulation materials, and structural eco-composites [\u003cspan citationid=\"CR50\" class=\"CitationRef\"\u003e50\u003c/span\u003e, \u003cspan citationid=\"CR51\" class=\"CitationRef\"\u003e51\u003c/span\u003e].\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec19\" class=\"Section2\"\u003e\n \u003ch2\u003eEffect of MTMS content on water contact angle (WCA)\u003c/h2\u003e\n \u003cp\u003eTo evaluate the effect of MTMS concentration on the hydrophobicity of cellulose\u0026ndash;silica composites, WCA measurements were carried out at various cellulose/MTMS molar ratios Fig. \u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e. The experiments were performed using either MCC or NCC as the substrate.\u003c/p\u003e\n \u003cp\u003eWhen MCC and NCC were used as cellulose sources, increasing the MTMS ratio relative to 1 mol of cellulose led to a gradual increase in WCA. For MCC-based composites, the WCA increased from 5\u0026deg; (1:1 and 1:1.2) to 40\u0026deg; (1:1.4), 80\u0026deg; (1:1.6), 100\u0026deg; (1:1.8), and finally 110\u0026deg; (1:2). In contrast, under the same conditions, NCC-based composites exhibited a much stronger hydrophobic response, with WCA values of 5\u0026deg; (1:1), 28\u0026deg; (1:1.2), 63\u0026deg; (1:1.4), 106\u0026deg; (1:1.6), 125\u0026deg; (1:1.8), and 126\u0026deg; (1:2), respectively.These results clearly demonstrate that increasing MTMS content enhances hydrophobicity in both MCC- and NCC -based systems, but the effect is more pronounced for NCC. The superior performance of NCC composites can be attributed to their higher specific surface area and nanoscale porosity, which provide more active sites for silanol condensation and siloxane network formation. As a result, NCC enables denser and more uniform hydrophobic surface coverage compared to MCC.\u003c/p\u003e\n \u003cp\u003eNotably, at cellulose-to-MTMS ratios of 1:1.8 and 1:2, the WCA values approach saturation, indicating that surface functionalization is nearly complete. For MCC, WCA values stabilized at ~\u0026thinsp;100\u0026ndash;110\u0026deg;, whereas CNC achieved values as high as 125\u0026ndash;126\u0026deg;, consistent with previously reported sol\u0026ndash;gel modified cellulose systems [\u003cspan citationid=\"CR52\" class=\"CitationRef\"\u003e52\u003c/span\u003e]. These findings underscore the critical role of cellulose morphology in determining the efficiency of silane grafting and the final hydrophobic performance of biocomposites.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec20\" class=\"Section2\"\u003e\n \u003ch2\u003eEffect of reaction temperature on water contact angle\u003c/h2\u003e\n \u003cp\u003eTo further investigate the influence of synthesis parameters on hydrophobicity, experiments were conducted at a fixed cellulose-to-MTMS molar ratio of 1:1.8 while systematically varying the reaction temperature from 20 to 100\u0026deg;C (20, 40, 60, 80, and 100\u0026deg;C). The hydrophobicity of MCC\u0026ndash;SiO₂ and NCC \u0026ndash;SiO₂ composites was evaluated by measuring static water contact angles Fig. \u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e.\u003c/p\u003e\n \u003cp\u003eThe WCA values increased progressively with temperature for both MCC- and NCC-based composites. This behaviour indicates that elevated reaction temperatures promote the condensation of hydrolyzed MTMS silanol groups with cellulose hydroxyl functionalities, leading to the formation of a denser and more uniform siloxane network. The NCC -based composites exhibited the highest hydrophobicity, reaching a maximum WCA of 136\u0026deg;\u0026plusmn; 1\u0026deg;, whereas MCC-based composites achieved a lower maximum of 120\u0026deg;\u0026plusmn; 1\u0026deg;. The superior performance of NCC is attributed to its higher surface-to-volume ratio, nanoscale porosity, and abundance of active hydroxyl groups, all of which facilitate more efficient surface functionalization and silane grafting. In contrast, MCC possesses fewer accessible sites, resulting in a less extensive siloxane network.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec21\" class=\"Section2\"\u003e\n \u003ch2\u003eEffect of reaction time on water contact angle\u003c/h2\u003e\n \u003cp\u003eTo complement these findings, the effect of reaction time was examined under optimized conditions (cellulose-to-MTMS ratio of 1:1.8 and temperature range of 80\u0026ndash;100\u0026deg;C). The reaction time was varied from 30 to 120 min to evaluate the kinetics of surface modification Fig. \u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003e. The experimental results revealed that extending the reaction duration beyond 60 min had only a minimal effect on WCA, with differences of ~\u0026thinsp;1\u0026ndash;2\u0026deg;. This indicates that the majority of MTMS condensation occurs within the initial 30\u0026ndash;60 min, after which the surface becomes nearly saturated with hydrophobic groups.\u003c/p\u003e\n \u003cp\u003eTherefore, a reaction time of 30\u0026ndash;60 min was identified as sufficient to achieve stable and effective hydrophobic modification. This not only improves time and energy efficiency but also enhances the practicality of the process for potential industrial-scale applications. Accordingly, subsequent experiments were carried out using 30 and 60 min as the standard reaction durations.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec22\" class=\"Section2\"\u003e\n \u003ch2\u003eTime-dependent stability of water contact angle\u003c/h2\u003e\n \u003cp\u003eTo evaluate the stability of surface hydrophobicity, the time-dependent change in WCA was investigated for composites obtained under optimized synthesis conditions and compared with their corresponding MCC and NCC precursors Fig. \u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003e.\u003c/p\u003e\n \u003cp\u003eFor pristine MCC, the initial contact angle was only 15\u0026deg;\u0026plusmn; 1\u0026deg;, which decreased rapidly to ~\u0026thinsp;3\u0026deg; within 20 min, indicating that the water droplet was quickly absorbed due to the strongly hydrophilic character of the cellulose surface. A similar trend was observed for NCC, where the initial contact angle of 15\u0026deg; \u0026plusmn; 1\u0026deg; dropped to ~\u0026thinsp;3\u0026deg; within 20 min, again reflecting its intrinsic hydrophilicity.\u003c/p\u003e\n \u003cp\u003eIn contrast, the cellulose\u0026ndash;silica composites demonstrated markedly different behavior. The MCC\u0026ndash;(CH₃SiO₁.₅)ₙ composite exhibited an initial WCA of 120\u0026deg;\u0026plusmn; 1\u0026deg;, which gradually decreased to 90\u0026deg; after 100 min. This result confirms that silica incorporation successfully imparted hydrophobicity to MCC, significantly reducing water absorption. Even more pronounced hydrophobic stability was observed in the NCC\u0026ndash;(CH₃SiO₁.₅)ₙ composite: its initial WCA of 136\u0026deg;\u0026plusmn; 1\u0026deg; decreased only to 120\u0026deg;\u0026plusmn; 1\u0026deg; after 100 min, indicating a highly stable hydrophobic surface.\u003c/p\u003e\n \u003cp\u003eThese findings demonstrate that while pristine cellulose precursors are strongly hydrophilic, their corresponding silica-based composites retain long-term hydrophobicity. The superior performance of NCC\u0026ndash;(CH₃SiO₁.₅)ₙ composites can be attributed to their higher surface area, nanoscale porosity, and more efficient silane grafting, which together provide a denser and more uniform hydrophobic siloxane coating.\u003c/p\u003e\n \u003cdiv id=\"Sec23\" class=\"Section3\"\u003e\n \u003ch2\u003eAnalysis of Benzene Sorption Isotherms of Cellulose\u0026ndash;Silica Composites\u003c/h2\u003e\n \u003cp\u003eThe cellulose\u0026ndash;silica composites synthesized via the sol\u0026ndash;gel method exhibit pronounced hydrophobic characteristics and significantly improved water-repellent properties, making them promising adsorbents for oil and petroleum-based contaminants.\u003c/p\u003e\n \u003cp\u003eFigure \u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e8\u003c/span\u003e presents the adsorption isotherms of MCC, NCC, MCC\u0026ndash;(CH₃SiO₁.₅)ₙ, NCC\u0026ndash;(CH₃SiO₁.₅)ₙ, and (CH₃SiO₁.₅)ₙ samples. In all cases, adsorption volumes increased gradually with relative pressure (P/P₀ = 0\u0026ndash;1), consistent with typical physisorption behavior.\u003c/p\u003e\n \u003cp\u003eAmong the tested materials, the MCC\u0026ndash; (CH₃SiO₁.₅)ₙ composite exhibited the highest adsorption capacity, reaching 5.3 cm\u0026sup3;/g at P/P₀ = 1. The NCC\u0026ndash;(CH₃SiO₁.₅)ₙ composite also showed enhanced adsorption performance (maximum 1.8 cm\u0026sup3;/g), although lower than MCC\u0026ndash;(CH₃SiO₁.₅)ₙ. In contrast, pristine MCC and NCC exhibited significantly lower adsorption volumes (0.88 cm\u0026sup3;/g and 0.26 cm\u0026sup3;/g, respectively). The pure (CH₃SiO₁.₅)ₙ sample prepared for comparison was synthesized via the sol\u0026ndash;gel method using MTMS as precursor. The (CH₃SiO₁.₅)ₙ reference sample displayed moderate capacity (1.4 cm\u0026sup3;/g), likely due to surface methylation, which limits the number of accessible adsorption sites.\u003c/p\u003e\n \u003cdiv class=\"gridtable\"\u003e\u0026nbsp;\u003ctable float=\"Yes\" id=\"Tab2\" border=\"1\"\u003e\n \u003ccaption language=\"En\"\u003e\n \u003cdiv class=\"CaptionNumber\"\u003eTable 2\u003c/div\u003e\n \u003cdiv class=\"CaptionContent\"\u003e\n \u003cp\u003eAdsorption isotherm parameters of cellulose, silica, and cellulose\u0026ndash;silica composites\u003c/p\u003e\n \u003c/div\u003e\n \u003c/caption\u003e\n \u003ccolgroup cols=\"7\"\u003e\u003c/colgroup\u003e\n \u003cthead\u003e\n \u003ctr\u003e\n \u003cth align=\"left\" colname=\"c1\"\u003e\n \u003cp\u003e№\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\" colname=\"c2\"\u003e\n \u003cp\u003eIndicators\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\" colname=\"c3\"\u003e\n \u003cp\u003eMCC\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\" colname=\"c4\"\u003e\n \u003cp\u003eMCC-(CH₃SiO₁.₅)ₙ\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\" colname=\"c5\"\u003e\n \u003cp\u003eNCC\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\" colname=\"c6\"\u003e\n \u003cp\u003eNCC-(CH₃SiO₁.₅)ₙ\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\" colname=\"c7\"\u003e\n \u003cp\u003e(CH₃SiO₁.₅)ₙ\u003c/p\u003e\n \u003c/th\u003e\n \u003c/tr\u003e\n \u003c/thead\u003e\n \u003ctbody\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" colname=\"c1\"\u003e\n \u003cp\u003e1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c2\"\u003e\n \u003cp\u003eA\u003csub\u003em\u003c/sub\u003e (monolayer capacity), mmol/g\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\n \u003cp\u003e0.26\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c4\"\u003e\n \u003cp\u003e1.8\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c5\"\u003e\n \u003cp\u003e0.07\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c6\"\u003e\n \u003cp\u003e0.6\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c7\"\u003e\n \u003cp\u003e0,4\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" colname=\"c1\"\u003e\n \u003cp\u003e2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c2\"\u003e\n \u003cp\u003eSpecific surface area S, m\u0026sup2;/g\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\n \u003cp\u003e61.7\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c4\"\u003e\n \u003cp\u003e432\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c5\"\u003e\n \u003cp\u003e15\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c6\"\u003e\n \u003cp\u003e147\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c7\"\u003e\n \u003cp\u003e94.4\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" colname=\"c1\"\u003e\n \u003cp\u003e3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c2\"\u003e\n \u003cp\u003eMicropore volume W\u003csub\u003emic\u003c/sub\u003e, cm\u0026sup3;/g\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\n \u003cp\u003e0.06\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c4\"\u003e\n \u003cp\u003e0.4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c5\"\u003e\n \u003cp\u003e0.02\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c6\"\u003e\n \u003cp\u003e0.12\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c7\"\u003e\n \u003cp\u003e0.08\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" colname=\"c1\"\u003e\n \u003cp\u003e4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c2\"\u003e\n \u003cp\u003eSaturation volume V\u003csub\u003es\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\n \u003cp\u003e0.08\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c4\"\u003e\n \u003cp\u003e0.5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c5\"\u003e\n \u003cp\u003e0.023\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c6\"\u003e\n \u003cp\u003e0.16\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c7\"\u003e\n \u003cp\u003e0.12\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" colname=\"c1\"\u003e\n \u003cp\u003e5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c2\"\u003e\n \u003cp\u003eMesopore volume W\u003csub\u003emezo\u003c/sub\u003e, cm\u0026sup3;/g\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\n \u003cp\u003e0.02\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c4\"\u003e\n \u003cp\u003e0,12\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c5\"\u003e\n \u003cp\u003e0.01\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c6\"\u003e\n \u003cp\u003e0,04\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c7\"\u003e\n \u003cp\u003e0.04\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" colname=\"c1\"\u003e\n \u003cp\u003e6\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c2\"\u003e\n \u003cp\u003ePore radius r\u003csub\u003ek\u003c/sub\u003e, \u0026Aring;\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\n \u003cp\u003e25.3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c4\"\u003e\n \u003cp\u003e21.5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c5\"\u003e\n \u003cp\u003e31.3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c6\"\u003e\n \u003cp\u003e21.5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\" colname=\"c7\"\u003e\n \u003cp\u003e25.8\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n \u003c/table\u003e\n \u003c/div\u003e\n \u003cp\u003eThe quantitative analysis presented in Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e further highlights the structural and adsorption advantages of silica-containing composites. The monolayer capacity (A\u003csub\u003em\u003c/sub\u003e) increased substantially after silica incorporation: from 0.26 \u0026rarr; 1.8 mmol/g for MCC and from 0.07 \u0026rarr; 0.6 mmol/g for NCC. Similarly, the specific surface area (S) expanded more than sevenfold for MCC\u0026ndash; (CH₃SiO₁.₅)ₙ (61.7 \u0026rarr; 432 m\u0026sup2;/g) and nearly tenfold for NCC \u0026ndash; (CH₃SiO₁.₅)ₙ (15 \u0026rarr; 147 m\u0026sup2;/g).\u003c/p\u003e\n \u003cp\u003eMicropore volume (W\u003csub\u003emic\u003c/sub\u003e) increased significantly (0.06 \u0026rarr; 0.4 cm\u0026sup3;/g for MCC; 0.02 \u0026rarr; 0.12 cm\u0026sup3;/g for CNC), indicating the formation of a more developed microporous network. The saturation volume (V\u003csub\u003es\u003c/sub\u003e) also rose sharply, particularly for MCC\u0026ndash;(CH₃SiO₁.₅)ₙ (0.5 cm\u0026sup3;/g), reflecting higher overall adsorption capacity. Additionally, mesopore volumes doubled or tripled in the composites, highlighting the synergistic contribution of mesoporosity to sorption efficiency.\u003c/p\u003e\n \u003cp\u003eInterestingly, a decrease in average pore radius was observed after silica modification (MCC: 25.3 \u0026Aring; \u0026rarr; MCC\u0026ndash;(CH₃SiO₁.₅)ₙ: 21.5 \u0026Aring;), suggesting the creation of smaller, more reactive pores, which improve adsorption kinetics. While pure (CH₃SiO₁.₅)ₙ did not exhibit the highest sorption, its balanced microporous and mesoporous structure confirms its utility as a supportive adsorbent.\u003c/p\u003e\n \u003cp\u003eOverall, the results clearly demonstrate that silica incorporation into cellulose significantly enhances specific surface area, microporosity, and sorption efficiency. MCC\u0026ndash;(CH₃SiO₁.₅)ₙ composites showed the highest performance, making them strong candidates for practical adsorbent applications.\u003c/p\u003e\n \u003cp\u003e\u003cstrong\u003eEvaluation of hydrophobic and oleophilic properties.\u003c/strong\u003e\u003c/p\u003e\n \u003cp\u003eThe hydrophobic and oleophilic properties of cellulose\u0026ndash;silica composites were evaluated using droplet tests Fig. \u003cspan refid=\"Fig9\" class=\"InternalRef\"\u003e9\u003c/span\u003e. The results clearly demonstrate that the composites simultaneously exhibit water-repellent and oil-attracting characteristics, which are crucial for their application as selective adsorbents.\u003c/p\u003e\n \u003cp\u003eWhen a water droplet was placed on the composite surface, it formed a contact angle greater than 130\u0026deg;, indicating strong hydrophobicity due to the low surface energy and the micro/nanostructured morphology of the material. Conversely, oil droplets spread and were rapidly absorbed into the composite, confirming its pronounced oleophilic behavior. Furthermore, in biphasic water\u0026ndash;oil systems, the cellulose\u0026ndash;silica composites selectively absorbed the oil phase while leaving the water phase unaffected. This pronounced selectivity confirms their strong potential for applications in oil spill remediation and oily wastewater treatment.\u003c/p\u003e\n \u003cp\u003eOverall, the results highlight the unique dual functionality of cellulose\u0026ndash;silica composites, which simultaneously exhibit hydrophobicity (water repellency) and oleophilicity (oil affinity). This combination makes them highly suitable for environmental remediation technologies, including oil spill clean-up, separation of organic pollutants from water, and the purification of industrial effluents.\u003c/p\u003e\n \u003c/div\u003e\n\u003c/div\u003e"},{"header":"Conclusion","content":"\u003cp\u003eIn this study, hydrophobic cellulose\u0026ndash;silica hybrid composites were successfully synthesized via a sustainable sol\u0026ndash;gel approach using microcrystalline (MCC) and nanocrystalline cellulose (NCC) derived from industrial licorice root waste as renewable biopolymer precursors. Methyltrimethoxysilane (MTMS) served both as a silica source and as an in situ hydrophobic modifier, enabling the formation of organically modified siloxane networks directly within the cellulose matrix.\u003c/p\u003e \u003cp\u003eFTIR analysis confirmed the formation of Si\u0026ndash;O\u0026ndash;Si and Si\u0026ndash;O\u0026ndash;C linkages, indicating effective chemical integration of silica into the cellulose structure, while the retention of \u0026ndash;CH₃ groups from MTMS provided reduced surface polarity and enhanced hydrophobicity. XRD results demonstrated a significant decrease in crystallinity (from 69% to 28% for MCC and from 78% to 32% for NCC), reflecting partial disruption of ordered cellulose domains due to silica incorporation and hybrid network formation. Thermogravimetric analysis revealed improved thermal stability of the composites, with degradation temperatures shifting toward higher values compared to pristine cellulose, confirming strong interfacial interactions between the organic and inorganic phases.\u003c/p\u003e \u003cp\u003eThe hydrophobic performance of the composites was strongly dependent on synthesis parameters. Under optimized conditions (cellulose-to-MTMS molar ratio 1:1.8, 80\u0026ndash;100\u0026deg;C, 30\u0026ndash;60 min), the water contact angle reached 120\u0026deg; \u0026plusmn; 1\u0026deg; for MCC-based composites and 136\u0026deg; \u0026plusmn; 1\u0026deg; for NCC-based composites, indicating highly stable hydrophobic surfaces. Time-dependent contact angle measurements further confirmed the durability of the hydrophobic modification, particularly for NCC\u0026ndash;(CH₃SiO₁.₅)ₙ composites.\u003c/p\u003e \u003cp\u003eBenzene adsorption studies demonstrated a substantial enhancement in adsorption capacity after silica incorporation. The specific surface area increased from 61.7 to 432 m\u0026sup2;/g for MCC-based composites and from 15 to 147 m\u0026sup2;/g for NCC-based composites, accompanied by a significant increase in micropore volume and monolayer adsorption capacity. Among the investigated samples, MCC\u0026ndash;(CH₃SiO₁.₅)ₙ exhibited the highest adsorption performance (5.3 cm\u0026sup3;/g at P/P₀ = 1), highlighting the synergistic effect of microstructure and silica-induced porosity.\u003c/p\u003e \u003cp\u003eThe obtained cellulose\u0026ndash;silica composites combine improved thermal stability, high hydrophobicity, developed porous structure, and strong oleophilic behavior, enabling selective oil adsorption from water\u0026ndash;oil systems. The use of biomass-derived cellulose from industrial waste further enhances the sustainability and environmental relevance of the developed materials.\u003c/p\u003e \u003cp\u003eOverall, this work demonstrates that sol\u0026ndash;gel hybridization with MTMS provides an efficient strategy for transforming hydrophilic cellulose into high-performance hydrophobic eco-sorbents. The developed materials show strong potential for applications in oil spill remediation, oily wastewater treatment, and environmentally friendly separation technologies.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eAcknowledgment\u0026nbsp;\u003c/strong\u003eThis study was supported by the Fundamental Program of the Academy of Sciences of the Republic of Uzbekistan\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAuthor Contributions\u0026nbsp;\u003c/strong\u003eАtakhanov A. Abdumutallib: Writing - Original Draft, Conceptualization; Ergashev J. Doniyor:\u003cstrong\u003e\u0026nbsp;\u003c/strong\u003eWriting - Original Draft, Formal analysis, Investigation, Methodology; Turdikulov Kh. Islom: Writing - Review \u0026amp; Editing;\u003cstrong\u003e\u0026nbsp;\u003c/strong\u003eYunusov E. Khaydar\u003cstrong\u003e:\u003c/strong\u003e\u003cstrong\u003e\u0026nbsp;\u003c/strong\u003eWriting\u0026nbsp;- Review \u0026amp; Editing Original Draft;\u0026nbsp;Guohua Jiang:\u0026nbsp;Writing\u0026nbsp;- Review \u0026amp; Editing; Xiaomin Zhu:\u0026nbsp;Writing - Review \u0026amp; Editing\u003cstrong\u003e.\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eFunding\u003c/strong\u003e This research was funded by the Ministry of Higher Education, Science and Innovation of the Republic of Uzbekistan under grant number AL-742210856.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eData Availability\u0026nbsp;\u003c/strong\u003eAll data that support the findings of this study are included within the article (and any supplementary files).\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eEthics approval and consent to participate\u0026nbsp;\u003c/strong\u003eNot applicable.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eConsent for publication\u0026nbsp;\u003c/strong\u003eNot applicable.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eConflict of Interest\u0026nbsp;\u003c/strong\u003eThe authors declare that there is no conflict of interests regarding the publication of this article.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eORCID\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eАtakhanov Abdumutallib Abdupatto ugli:\u003cstrong\u003e\u0026nbsp;\u003c/strong\u003ehttps://orcid.org/0000-0002-4975-3658\u003c/p\u003e\n\u003cp\u003eErgashev Doniyor Jabborovich: https://orcid.org/0000-0003-4547-9142 \u0026nbsp;\u003c/p\u003e\n\u003cp\u003eTurdikulov Islom\u003cstrong\u003e\u0026nbsp;\u003c/strong\u003eHayitboy o\u0026rsquo;g\u0026rsquo;li:\u003cstrong\u003e\u0026nbsp;\u003c/strong\u003ehttps://orcid.org/0000-0001-5100-7729\u003c/p\u003e\n\u003cp\u003eYunusov Khaydar Ergashovich: https://orcid.org/0000-0002-4646-7859 \u0026nbsp;\u003c/p\u003e\n\u003cp\u003eGuohua Jiang: https://orcid.org/0000-0003-3666-8216\u003c/p\u003e\n\u003cp\u003eXiaomin Zhu: \u0026nbsp;https://orcid.org/0000-0002-3887-6791\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eWu W, Yang Y, Zhang J, Lu J (2018) Study on striking ship with loading impact on the performance of the double hull oil tanker collision. Pol Maritime Res. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.2478/pomr-2018-0072\u003c/span\u003e\u003cspan address=\"10.2478/pomr-2018-0072\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eNguyen XP, Nguyen DT, Pham VV, Vo DT (2022) Highlights of oil treatment technologies and rise of oil-absorbing materials in ocean cleaning strategy. Water Conserv Manag. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.26480/wcm.01.2022.06.14\u003c/span\u003e\u003cspan address=\"10.26480/wcm.01.2022.06.14\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eLang D, Zhang C, Qian Q, Guo C, Wang L, Yang C et al (2023) Oil absorption stability of modified cellulose porous materials with super compressive strength in the complex environment. Cellulose. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1007/s10570-023-05322-5\u003c/span\u003e\u003cspan address=\"10.1007/s10570-023-05322-5\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eWang X, Li X Preparation of superhydrophobic membranes with ultraviolet-absorbing capacity for oil\u0026ndash;water separation by electrospinning. Polym Eng Sci. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1002/pen.26670\u003c/span\u003e\u003cspan address=\"10.1002/pen.26670\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eBilal M, Shafiqur MR, Chunbao CX, Tingheng Z, Qin W (2024) Environmental impact associated with oil and grease and their emerging mitigation strategies. J Clean Prod. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1007/s12649-024-02425-3\u003c/span\u003e\u003cspan address=\"10.1007/s12649-024-02425-3\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eLiew YX, Chan YJ, Manickam S, Chong MF, Chong S, Tiong TJ, Lim JW, Pan GT (2020) Enzymatic pretreatment to enhance anaerobic bioconversion of high strength wastewater to biogas: A review. Sci Total Environ. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.scitotenv.2019.136373\u003c/span\u003e\u003cspan address=\"10.1016/j.scitotenv.2019.136373\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eZhang G, Zhan Y, He S, Zhang L, Zeng G, Chiao YH (2020) Construction of superhydrophilic/underwater superoleophobic polydopamine-modified h-BN/poly(arylene ether nitrile) composite membrane for stable oil-water emulsions separation. Polym Adv Technol. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1002/pat.4835\u003c/span\u003e\u003cspan address=\"10.1002/pat.4835\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eZhao YH, Guo JX, Zhang XN, An AK, Wang ZK (2022) Superhydrophobic and superoleophilic pH-CNT membrane for emulsified oil-water separation. Desalination. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.desal.2022.115536\u003c/span\u003e\u003cspan address=\"10.1016/j.desal.2022.115536\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eWang H, Guo X, Pei C, Dong W, Yao Y (2022) Hydrophilic modification of polypropylene membrane via tannic and titanium complexation for high efficiency oil/water emulsion separation driven by self gravity. Polym Eng Sci. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1002/pen.25994\u003c/span\u003e\u003cspan address=\"10.1002/pen.25994\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eWoo S, Park HR, Yi Park J, Hwang JW (2020) Robust and continuous oil/water separation with superhydrophobic glass microfiber membrane by vertical polymerization under harsh conditions. Sci Rep. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1038/s41598-020-78440-3\u003c/span\u003e\u003cspan address=\"10.1038/s41598-020-78440-3\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eDmitrieva ES, Anokhina TS, Novitsky EG, Volkov VV, Borisov IL, Volkov AV (2022) Polymeric membranes for oil-water separation: A review. Polymers. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.3390/polym14050980\u003c/span\u003e\u003cspan address=\"10.3390/polym14050980\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eGuo YQ, Xu C, Liu GL, Xiao K, Zhao HZ (2021) Interpenetrating network nanoarchitectonics of antifouling poly(vinylidene fluoride) membranes for oil-water separation. RSC Adv. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1039/D1RA05450H\u003c/span\u003e\u003cspan address=\"10.1039/D1RA05450H\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eXu QJ, Tian XL, Jin XG, Wu LL (2021) Inner surface hydrophilic modification of PVDF membrane with tea polyphenols/silica composite coating. Polymers. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.3390/polym13234186\u003c/span\u003e\u003cspan address=\"10.3390/polym13234186\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eOlabintan AB, Ahmed EA, Abdulgader H, Saleh TA (2022) Hydrophobic and oleophilic amine-functionalised graphene/polyethylene nanocomposite for oil-water separation. Environ Technol Innov. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.eti.2022.102391\u003c/span\u003e\u003cspan address=\"10.1016/j.eti.2022.102391\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eZhang T, Li Z, L\u0026uuml; Y, Liu Y, Yang D, Li Q, Qiu F (2019) Recent progress and future prospects of oil-absorbing materials. Chin J Chem Eng. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.cjche.2018.09.001\u003c/span\u003e\u003cspan address=\"10.1016/j.cjche.2018.09.001\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eLin YM, Song C, Rutledge GC (2019) Functionalization of electrospun membranes with polyelectrolytes for separation of oil-in-water emulsions. Adv Mater Interfaces 6(20):1901285. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1002/admi.201901285\u003c/span\u003e\u003cspan address=\"10.1002/admi.201901285\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eKhajehamidi M, Gharehaghaji AA, Harifi T (2026) Hydrophobic breathable electrospun nanofibrous PU membranes: An insight into the effect of Si nanoparticles and NaCl. J Polym Res. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1007/s10965-025-04725-1\u003c/span\u003e\u003cspan address=\"10.1007/s10965-025-04725-1\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eBhagyaraj S, Sobolciak P, Al-Ghouti MA, Krupa I (2021) Copolyamide-clay nanotube polymer composite nanofiber membranes: preparation, characterization and its asymmetric wettability driven oil/water emulsion separation towards sewage remediation. Polymers. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.3390/polym13213710\u003c/span\u003e\u003cspan address=\"10.3390/polym13213710\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eSuzuki R (2024) Effect of adding bentonite to porous silica via the sol\u0026ndash;gel method. ACS Omega. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1021/acsomega.3c08832\u003c/span\u003e\u003cspan address=\"10.1021/acsomega.3c08832\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eBarud HS, Assuncao RM, Martines MA, Dexpert-Ghys J, Marques RFC, Messaddeq Y, Ribeiro SJL (2008) Bacterial cellulose\u0026ndash;silica organic\u0026ndash;inorganic hybrids. J Solgel Sci Technol. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1007/s10971-007-1669-9\u003c/span\u003e\u003cspan address=\"10.1007/s10971-007-1669-9\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eSonia S, Dmitry VE, Ines P, Ana EP (2007) Synthesis and characterization of cellulose/silica hybrids obtained by heteropoly acid catalysed sol\u0026ndash;gel process. Mater Sci Eng C. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.msec.2006.04.007\u003c/span\u003e\u003cspan address=\"10.1016/j.msec.2006.04.007\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eHammouda SB et al (2021) Recent advances in developing cellulosic sorbent materials for oil spill cleanup: A state-of-the-art review. J Clean Prod. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.jclepro.2021.127630\u003c/span\u003e\u003cspan address=\"10.1016/j.jclepro.2021.127630\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eYuldoshov SA, Yunusov KE, Sarymsakov AA, Goyibnazarov IS (2022) Synthesis and characterization of sodium carboxymethylcellulose from cotton, powder, microcrystalline and nanocellulose. Polym Eng Sci. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1002/pen.25874\u003c/span\u003e\u003cspan address=\"10.1002/pen.25874\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eAtakhanov AA, Kholmuminov AA, Mamadiyorov BN, Turdikulov IK, Ashurov NS (2020) Rheological behavior of nanocellulose aqueous suspensions. Polym Sci Ser A. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1134/S0965545X20030013\u003c/span\u003e\u003cspan address=\"10.1134/S0965545X20030013\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eAggarwal P, Maji S, Purwar R (2026) Structure\u0026ndash;property relationships in high-density flexible polyurethane foams reinforced with cellulose nanocrystals (CNC): Comparative effects of particle size. J Polym Res. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1007/s10965-026-03137-5\u003c/span\u003e\u003cspan address=\"10.1007/s10965-026-03137-5\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eAtakhanov AA, Mamadiyorov B, Kuzieva M, Yugai SM, Shakhobutdinov S, Ashurov NS (2019) Comparative studies of the physicochemical properties and structure of cotton cellulose and its modified forms. Chem Plant Raw Mater. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.14258/jcprm.2019034554\u003c/span\u003e\u003cspan address=\"10.14258/jcprm.2019034554\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eMamadiyorov BN, Ergashev DJ, Saidmukhammadova MQ, Ashurov NS, Atakhanov AA (2022) Preparation of micro- and nanocrystalline cellulose from straw cellulose and investigation of its properties. Sci J Sci Innovative Dev. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.36522/2181-9637-2022-4-1\u003c/span\u003e\u003cspan address=\"10.36522/2181-9637-2022-4-1\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eKuzieva MA, Atakhanov AA, S, hakhobutdinov SS, Ashurov NS, Yunusov KE, Guohua J (2023) Preparation of oxidized nanocellulose by using potassium dichromate. Cellulose. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1007/s10570-023-05222-8\u003c/span\u003e\u003cspan address=\"10.1007/s10570-023-05222-8\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eMorais JPS, Rosa MF, Filho MMS, Nascimento LD, Nascimento DM, Cassales AR (2013) Extraction and characterization of nanocellulose structures from raw cotton linter. Carbohydr Polym. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.carbpol.2012.08.010\u003c/span\u003e\u003cspan address=\"10.1016/j.carbpol.2012.08.010\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eSuhas VK, Gupta PJ, Carrott M, Chaudhary M, Kushwaha S (2016) Cellulose: a review as natural, modified and activated carbon adsorbent. Bioresour Technol. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.biortech.2016.05.106\u003c/span\u003e\u003cspan address=\"10.1016/j.biortech.2016.05.106\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eAn Y et al (2024) Hydrophobic modification of cellulose acetate and its application in the field of water treatment: A review. Molecules. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.3390/molecules29215127\u003c/span\u003e\u003cspan address=\"10.3390/molecules29215127\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eChen L et al (2018) Water adsorption on hydrophilic and hydrophobic surfaces of silicon. J Phys Chem C. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1021/acs.jpcc.8b01821\u003c/span\u003e\u003cspan address=\"10.1021/acs.jpcc.8b01821\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eJia W, Tian J, Liu W, Niu J, Zhang J, Junchao L, Li J, Yu X, Gao H (2025) Research progress and applications of cellulose-based functional materials. Polym Adv Technol. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1002/pat.70318\u003c/span\u003e\u003cspan address=\"10.1002/pat.70318\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eDarmakkolla SR et al (2016) A method to derivatize surface silanol groups to Si-alkyl groups in carbon-doped silicon oxides. RSC Adv. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1039/C6RA20355H\u003c/span\u003e\u003cspan address=\"10.1039/C6RA20355H\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eLuo T et al (2021) Hydrophobic modification of silica surfaces via grafting alkoxy groups. ACS Appl Electron Mater. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1021/acsaelm.1c00017\u003c/span\u003e\u003cspan address=\"10.1021/acsaelm.1c00017\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003ePinto RB, Marques PA, Barros-Timmons AM, Trindade T, Neto CP (2008) Novel SiO₂/cellulose nanocomposites obtained by in situ synthesis and via polyelectrolytes assembly. Compos Sci Technol. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.compscitech.2007.03.001\u003c/span\u003e\u003cspan address=\"10.1016/j.compscitech.2007.03.001\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eHribernik S, Smole MS, Kleinschek KS, Bele M, Jamnik J, Gaberscek M (2007) Flame retardant activity of SiO₂-coated regenerated cellulose fibres. Polym Degrad Stab. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.polymdegradstab.2007.08.010\u003c/span\u003e\u003cspan address=\"10.1016/j.polymdegradstab.2007.08.010\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eRosaria C, Alexandra F, Valerica P, Fran\u0026ccedil;ois BL, Laura MI, Mario P (2013) The sol\u0026ndash;gel route to advanced silica-based materials and recent applications. Chem Rev. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1021/cr300399c\u003c/span\u003e\u003cspan address=\"10.1021/cr300399c\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eLavorgna M, Verdolotti L, Mascia L (2015) Organic\u0026ndash;inorganic bio-hybrid materials by sol\u0026ndash;gel processing. Biofoams: Science and Applications of Bio-Based Cellular and Porous Materials. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1039/D1CS00519G\u003c/span\u003e\u003cspan address=\"10.1039/D1CS00519G\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eShange MG et al (2024) Factors affecting silica/cellulose nanocomposite prepared via the sol\u0026ndash;gel technique: A review. Materials. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.3390/ma17091937\u003c/span\u003e\u003cspan address=\"10.3390/ma17091937\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eHussain A, Calabria-Holley J, Schorr D, Jiang Y, Lawrence BP (2018) Hydrophobicity of hemp shiv treated with sol\u0026ndash;gel coatings. Appl Surf Sci. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.apsusc.2017.10.210\u003c/span\u003e\u003cspan address=\"10.1016/j.apsusc.2017.10.210\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eTan B, Rankin SE (2006) Study of the effects of progressive changes in alkoxysilane structure on sol\u0026ndash;gel reactivity. J Phys Chem B. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1021/jp060376k\u003c/span\u003e\u003cspan address=\"10.1021/jp060376k\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eChrusciel JJ, Lesniak E (2015) Modification of epoxy resins with functional silanes, polysiloxanes, silsesquioxanes, silica and silicates. Prog Polym Sci. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.progpolymsci.2014.08.001\u003c/span\u003e\u003cspan address=\"10.1016/j.progpolymsci.2014.08.001\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eVasquez A, Cyras VP, Alvarez VA, Moran JI (2012) Starch/clay nano-biocomposites. In: Averous L, Pollet E (eds) Environmental Silicate Nano-Biocomposites. Springer, London, UK. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1155/2015/493439\u003c/span\u003e\u003cspan address=\"10.1155/2015/493439\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eShakhabutdinov SS, Yugay SM, Ashurov NS, Ergashev DJ, Atakhanov AA, Rashidova SS (2024) Characterization of electrospun nanofibers based on cellulose triacetate synthesized from licorice root cellulose. Eurasian J Chem. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.31489/2959-0663/2-24-2\u003c/span\u003e\u003cspan address=\"10.31489/2959-0663/2-24-2\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eKyung-Soo K, Jun-Kyung K, Woo-Sik K (2002) Influence of reaction conditions on sol-precipitation process producing silicon oxide particles. Ceram Int. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/S0272-8842(01)00076-1\u003c/span\u003e\u003cspan address=\"10.1016/S0272-8842(01)00076-1\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eMasoud M, Malihe BZ, Mahdieh D, Khalilollah S, Seyed TK, Jalil S, Azadeh F, Hajar M (2020) Silica mesoporous structures: Effective nanocarriers in drug delivery and nanocatalysts. Appl Sci. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.3390/app10217533\u003c/span\u003e\u003cspan address=\"10.3390/app10217533\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eJoabel R, Alessandra SF, Lina B, Caue R, Maria AM, Jose MM, Gustavo H, Denzin T (2014) Evaluation of reaction factors for deposition of silica (SiO₂) nanoparticles on cellulose fibers. Carbohydr Polym. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.carbpol.2014.08.042\u003c/span\u003e\u003cspan address=\"10.1016/j.carbpol.2014.08.042\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eMusawenkosi GS, Nduduzo LK, Samson MM, Tshwafo EM (2024) Factors affecting silica/cellulose nanocomposite prepared via the sol\u0026ndash;gel technique: A review. Materials. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.3390/ma17091937\u003c/span\u003e\u003cspan address=\"10.3390/ma17091937\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eLu J, Shi J, Guo LW, Zhang J, Cao Y (2013) Heat insulation performance, mechanics and hydrophobic modification of cellulose\u0026ndash;SiO₂ composite aerogels. Carbohydr Polym. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.carbpol.2013.05.082\u003c/span\u003e\u003cspan address=\"10.1016/j.carbpol.2013.05.082\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eNing J, Shu-Ming S, Ming-Guo M, Jie-Fang J, Run-Cang S (2011) Synthesis of cellulose silica composite. BioResources. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.15376/biores.6.2.1186-1195\u003c/span\u003e\u003cspan address=\"10.15376/biores.6.2.1186-1195\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eFan S, Kunthom R, Meng Y, Kostjuk SV, Liu H (2025) Superhydrophobic fabric coated with double-decker silsesquioxane-based hybrid polymer for efficient oil/water separation and enhanced antifouling performance. Cellulose. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1007/s10570-025-05585-6\u003c/span\u003e\u003cspan address=\"10.1007/s10570-025-05585-6\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"journal-of-polymer-research","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"jpol","sideBox":"Learn more about [Journal of Polymer Research](https://www.springer.com/journal/10965)","snPcode":"10965","submissionUrl":"https://www.editorialmanager.com/jpol/","title":"Journal of Polymer Research","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"Cellulose nanocrystals, microcrystalline cellulose, cellulose–silica composites, sol–gel hybrid materials, surface modification, eco-sorbents","lastPublishedDoi":"10.21203/rs.3.rs-9245876/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-9245876/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eThe synthesis of hydrophobic cellulose\u0026ndash;silica composites was accomplished via a sol\u0026ndash;gel route. Cellulose obtained from industrial licorice-root waste, an inexpensive raw material, was used as a renewable precursor in its microcrystalline (MCC) and nanocrystalline (NCC) forms. Methyltrimethoxysilane (MTMS) was employed as the silicon source as well as the hydrophobic modifying agent. During the study, the effects of the MCC and NCC/MTMS molar ratio, reaction temperature, and reaction time on composite formation were systematically investigated. The results showed that a molar ratio of MCC and NCC/MTMS of 1:1.8, a reaction temperature of 80\u0026ndash;100\u0026deg;C, and a reaction duration of 60 minutes represented the optimal conditions for composite formation. The composites synthesized under these optimized parameters exhibited pronounced hydrophobic properties. The water contact angles of pristine microcrystalline cellulose (MCC) and nanocrystalline cellulose (NCC) were determined to be 15\u0026deg; \u0026plusmn; 1\u0026deg;, indicating their intrinsically hydrophilic nature. In contrast, after silica modification, the water contact angle increased significantly to 120\u0026deg; \u0026plusmn; 1\u0026deg; for the MCC\u0026ndash;(CH₃SiO₁.₅)ₙ composite and to 136\u0026deg; \u0026plusmn; 1\u0026deg; for the NCC\u0026ndash;(CH₃SiO₁.₅)ₙ composite, confirming the successful formation of hydrophobic surfaces. Furthermore, benzene adsorption isotherms were investigated to evaluate the adsorption performance of the materials. At a relative pressure of P/P₀ = 1, the adsorption capacity of pristine MCC and NCC was found to be 0.88 cm\u0026sup3;/g and 0.26 cm\u0026sup3;/g, respectively. After composite formation, these values increased markedly to 5.3 cm\u0026sup3;/g for the MCC\u0026ndash;(CH₃SiO₁.₅)ₙ composite and 1.8 cm\u0026sup3;/g for the NCC\u0026ndash;(CH₃SiO₁.₅)ₙ composite, demonstrating a substantial enhancement in adsorption capacity as a result of silica incorporation and surface hydrophobization. The structural and thermal properties were evaluated using X-ray diffraction (XRD), thermogravimetric analysis (TGA), and Fourier-transform infrared spectroscopy (FTIR). Additionally, the hydrophobicity and oil/grease adsorption efficiency were assessed. The resulting materials exhibited enhanced water repellency, high thermal stability, and superior adsorption capacity for oil and grease. The utilization of cellulose\u0026ndash;silica composites as sustainable adsorbents for the remediation of hydrocarbon-based pollutants is a promising avenue for environmental restoration. These composites are notable for their eco-friendly origin and demonstrated efficacy, which underscores their significant potential in addressing environmental concerns.\u003c/p\u003e","manuscriptTitle":"Micro- and nanocellulose-based silica hybrid nanocomposites as eco-sorbents for efficient oil removal","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2026-04-09 14:56:24","doi":"10.21203/rs.3.rs-9245876/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"reviewerAgreed","content":"","date":"2026-04-03T14:02:33+00:00","index":0,"fulltext":""},{"type":"reviewersInvited","content":"","date":"2026-04-03T09:06:40+00:00","index":"","fulltext":""},{"type":"editorInvited","content":"Journal of Polymer Research","date":"2026-04-03T03:15:11+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2026-03-30T12:39:12+00:00","index":"","fulltext":""},{"type":"submitted","content":"Journal of Polymer Research","date":"2026-03-27T10:31:59+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"journal-of-polymer-research","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"jpol","sideBox":"Learn more about [Journal of Polymer Research](https://www.springer.com/journal/10965)","snPcode":"10965","submissionUrl":"https://www.editorialmanager.com/jpol/","title":"Journal of Polymer Research","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"1b3099cd-0782-43d0-93e8-7a2cb03e0b7b","owner":[],"postedDate":"April 9th, 2026","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"under-review","subjectAreas":[],"tags":[],"updatedAt":"2026-04-09T14:56:24+00:00","versionOfRecord":[],"versionCreatedAt":"2026-04-09 14:56:24","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-9245876","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-9245876","identity":"rs-9245876","version":["v1"]},"buildId":"XKTyCvWXoU3ODBz1xrDgd","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}