The surface Reactivity of Silver Nanoparticles Doped with TiO 2 Nanorod like crystals for enhancing Photocatalytic Degradation of harmful water pollutants under visible - light irradiations

The surface Reactivity of Silver Nanoparticles Doped with TiO 2 Nanorod like crystals for enhancing Photocatalytic Degradation of harmful water pollutants under visible - light irradiations | 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 The surface Reactivity of Silver Nanoparticles Doped with TiO 2 Nanorod like crystals for enhancing Photocatalytic Degradation of harmful water pollutants under visible - light irradiations P. Govindhan, A. Sivaprakasam, T Chandrasekaran, S. Sivaraman, and 2 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-8839922/v1 This work is licensed under a CC BY 4.0 License Status: Under Revision Version 1 posted 10 You are reading this latest preprint version Abstract A novel photocatalyst was developed through the synthesis of TiO₂ nanoparticles followed by their transformation into TiO₂ nanorod-like crystals via a hydrothermal method. The surface properties of this TiO₂ nanorod like crystals (TiO₂ NRCs) were further enhanced by decorating them with Ag nanoparticles using a chemical reduction approach, resulting in a significant improvement in photocatalytic performance of TiO₂–Ag NRCs. To elucidate the origin of this enhancement, a comprehensive investigation of the structural, optical, vibrational, and electrochemical properties was carried out using a range of advanced characterization techniques, including high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), diffuse reflectance spectroscopy (DRS), photoluminescence spectroscopy (PL), electrochemical impedance spectroscopy (EIS), Fourier transform infrared spectroscopy (FTIR), UV–visible spectroscopy, and Raman spectroscopy. HRTEM analysis confirmed the successful formation of heterojunctions within the photocatalyst, revealing the intimate interfacial contact and uniform decoration of Ag nanoparticles on the surface of TiO₂ nanorod like crystals. XRD patterns demonstrated the highly crystalline nature of the synthesized materials, while EIS measurements indicated enhanced separation and transport of photogenerated charge carriers. The improved charge dynamics are attributed to the efficient transfer of electrons from the conduction band of TiO₂ to Ag nanoparticles, which suppresses electron–hole recombination and prolongs the lifetime of holes within the TiO₂ NRCs. The photocatalytic activity of the TiO₂–Ag NRCs was systematically evaluated and compared with that of pristine TiO₂ nanoparticles through the degradation of methylene blue dye in an aqueous medium, monitored using UV–visible spectroscopy. The one-dimensional TiO₂–Ag nanorod-like crystals exhibited superior photocatalytic efficiency, achieving an exceptional methylene blue degradation efficiency of 99.7%. These results highlight the remarkable potential of TiO₂–Ag NRCs as highly efficient photocatalysts for the removal of organic pollutants and their promising applicability in addressing serious environmental water contamination challenges. TiO2 NPs Ag-TiO2 NRCs nanocomposite Photocatalyst Dye degradation Methylene Blue Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 Figure 9 Figure 10 1. Introduction Over the past decades, titanium dioxide (TiO₂) has attracted significant attention due to its wide range of applications in photocatalysis, water purification, sensor technology, and dye-sensitized solar cells, owing to its chemical stability, low toxicity, and cost-effectiveness [ 1 – 3 ]. TiO₂ possesses a wide band gap of approximately 3.0 eV for the rutile phase and 3.2 eV for the anatase phase, enabling efficient excitation of electrons from the valence band to the conduction band under ultraviolet irradiation. The growing dependence on photocatalysts and solar-energy-driven technologies has highlighted advanced oxidation processes as promising alternatives for environmental remediation, underscoring the importance of developing sustainable and efficient materials [ 4 – 6 ]. TiO₂ nanoparticles exist in three distinct crystalline phases: anatase, brookite, and rutile. Among these, the rutile phase is thermodynamically more stable, whereas anatase and brookite are metastable. Phase transformations between these structures are influenced by several factors, including particle size, pH, surface area, and solution composition [ 7 , 8 ]. TiO₂ is regarded as a novel and versatile material due to its high adsorption capacity, which enhances dye molecule uptake. However, increasing the dopant concentration beyond an optimal level can lead to the formation of secondary phases, resulting in reduced visible-light absorption due to increased electron–hole recombination [ 9 – 14 ]. Surface morphology modifications induced by metal doping (e.g., Au, Ag, and Pt) in TiO₂ nanostructures such as nanoparticles, nanotubes, nanorods, and nanospheres have been shown to broaden visible-light absorption and significantly enhance photocatalytic activity. Among these structures, TiO₂ nanotubes exhibit superior photocatalytic performance compared to TiO₂ nanoparticles, attributed to their higher specific surface area and improved crystalline order. Furthermore, the deposition of silver nanoparticles on TiO₂ surfaces markedly enhances photocatalytic degradation rates through localized surface plasmon resonance effects and efficient charge separation at the Ag/TiO₂ interface [ 15 – 19 ]. Ag/TiO₂ composite materials have been extensively studied for photocatalytic applications and also demonstrate considerable potential in heterogeneous catalysis, dye-sensitized solar cells, photovoltaic devices, sensors, adsorption processes, and surface coatings due to their favorable surface morphology and electronic properties [ 20 – 22 ]. In addition, surface modification of TiO₂ into low-dimensional nanostructures (1D and 2D) improves photoelectric conversion efficiency through enhanced light harvesting, multilevel scattering, and accelerated electron transport. Recent studies have further expanded TiO₂ functionality by integrating it with materials such as polymers, graphene oxide, and carbon nanotubes [ 23 – 25 ]. The catalytic activity of TiO₂-based composites is particularly significant in immobilization strategies involving oxide heterostructures, including TiO₂@Fe₃O₄ [ 26 ], TiO₂@SiO₂ [ 27 ], ZnO@TiO₂ [ 28 ], and TiO₂@Fe₃O₄@SiO₂. These composite systems exhibit improved charge separation and enhanced photocatalytic performance, particularly under visible-light irradiation. In this study, TiO₂ nanoparticles were synthesized via a sol–gel method and subsequently modified to form silver-decorated TiO₂ nanocrystal composites (Ag–TiO₂ NRCs). The photocatalytic efficiency of these materials was evaluated through the degradation of methylene blue dye under sunlight irradiation, demonstrating their significant potential for environmental remediation applications. 2. Experimental methods: 2.1. Materials: Titanium(IV) chloride, titanium isopropoxide (TTIP), ammonium hydroxide (NH₄OH), sodium hydroxide (NaOH), hydrochloric acid (HCl), perchloric acid (HClO₄), ethylene glycol (EG), and polyvinylpyrrolidone (PVP) were procured from Merck Chemicals and used as precursor materials for the synthesis of various titanium dioxide nanostructures, including nanoparticles, nanospheres, and nanorods. Silver nitrate (AgNO₃, 99.9% purity), obtained from Sigma-Aldrich, and was employed as the precursor for the synthesis of silver nanoparticles. All chemicals were of analytical grade and were used without further purification. Double-distilled water was used throughout the experiments for the preparation of aqueous solutions and for washing processes unless otherwise specified. 2.2. Synthesis of TiO 2 Nanorod Crystals (TiO 2 NRCs) The synthesized TiO₂ nanoparticles were prepared according to our previous work [ 54 ]. TiO₂ nanorod-like crystals (TiO₂ NRCs) were synthesized using a carefully controlled procedure emphasizing precision and proper handling of chemical materials. Initially, 20 mL of 2 N mixed hydroxide solution, composed of NaOH and KOH in an equal ratio, was transferred into a 50 mL Teflon-lined vessel and sealed with a cover to prevent dust contamination. Subsequently, 1 g of the synthesized TiO₂ nanoparticles was gently placed onto the hydroxide solution inside the vessel. The sealed vessel was then heated in a furnace at 200°C for 3 h. During this stage, the vessel was periodically agitated to ensure uniform mixing of the reactants. Afterward, the sample was returned to the furnace and maintained at 200°C for an additional 36 h to facilitate further crystal growth and chemical interaction. Upon completion of the heating process, the product was washed repeatedly with 0.1 M HCl solution followed by distilled water until a neutral pH (≈ 7.0) was achieved. Finally, the obtained material was calcined at various temperatures to stabilize and enhance the crystalline structure. For comparison, an additional sample was prepared following the same synthesis protocol but washed exclusively with distilled water. This comparison highlights the influence of the washing process on the structural and physicochemical properties of the resulting TiO₂ NRCs. 2.3. Synthesis of TiO₂ –Ag Nanorod Crystals (NRCs) Silver nanoparticles were deposited onto TiO₂ nanorod-like crystals (NRCs) via a chemical reduction method, in which Ag⁺ ions were reduced to metallic Ag nanoparticles. Briefly, 1 g of pre-synthesized TiO₂ NRCs was dispersed in 250 mL of double-distilled water and stirred continuously for 30 min to achieve a homogeneous suspension. Subsequently, Ag⁺ ions (4 wt%) were added under constant stirring. The reduction of Ag⁺ was carried out by the dropwise addition of NaBH₄ until a greenish-yellow coloration appeared, indicating the formation of TiO₂–Ag NRC nanocomposites. The reaction mixture was further stirred for 30 min to ensure complete reduction and uniform deposition of Ag nanoparticles. The resulting nanocomposites were collected by filtration, thoroughly washed with double-distilled water, and dried at 60°C for 3 h. Finally, the dried samples were calcined at 450°C for 3 h to obtain the TiO₂–Ag NRC nanocomposites (Scheme 1). 2.4. Characterization Studies The optical absorption properties of various TiO₂ nanostructures and TiO₂–Ag ₂ NRC catalysts were investigated using a UV–vis spectrophotometer (Shimadzu UV-2550). Diffuse reflectance spectra (DRS) of pristine TiO₂ nanoparticle powders and TiO₂–Ag NRC nanocomposites were recorded using an ISR-2200 DRS accessory attached to the same instrument. Powder X-ray diffraction (XRD) patterns were obtained using a Scintag XDS-2000 diffractometer with Cu Kα radiation (λ = 1.5406 Å), operated at 40 kV and 30 mA. The morphology and particle size of the nanomaterials were examined by high-resolution transmission electron microscopy (HRTEM). SEM images were acquired using a TESCAN VEGA3 microscope, while TEM images were recorded on an FEI transmission electron microscope operating at an accelerating voltage of 200 kV. Raman spectra were collected in the range of 300–1000 cm⁻¹ using a JASCO-3100 laser Raman spectrometer. Photoluminescence (PL) spectra were measured using a Fluoromax-4 spectrofluorometer with an excitation wavelength of 325 nm to evaluate the charge carrier recombination behavior and photocatalytic performance of the TiO₂–Ag NRC nanocomposites. Electrochemical impedance spectroscopy (EIS) measurements were carried out using a potentiostat (model EIS-650) to analyze charge transfer characteristics. Fourier transform infrared (FTIR) spectra were recorded using a Shimadzu FT-IR-650 spectrometer in the KBr pellet mode to identify the functional groups present in the TiO₂–Ag NRC nanocomposites. 2.5. Photocatalytic activity measurement The photocatalytic performance of silver-decorated TiO₂ nanoparticles (TiO₂ NPs), TiO₂ nanorod clusters (TiO₂ NRCs), TiO₂–Ag NPs, and TiO₂–Ag NRCs was evaluated via the degradation of methylene blue (MB) dye under natural sunlight irradiation. To ensure experimental accuracy, the reaction vessel was placed inside a sealed black box equipped with a top opening to allow controlled exposure to visible light. For each experiment, 0.05 g of the photocatalyst was dispersed in 100 mL of methylene blue solution with a concentration of 1.05 g L⁻¹. The suspension was first ultrasonicated for 5 min to achieve uniform dispersion, followed by magnetic stirring in the dark for 30 min to establish adsorption–desorption equilibrium between the dye molecules and the photocatalyst surface. Afterward, the reaction mixture was exposed to direct sunlight during daytime hours (11:00 am 2:00 pm), corresponding to the period of maximum solar intensity. At predetermined time intervals, aliquots were withdrawn, and the residual dye concentration was analyzed using a UV–Vis spectrophotometer. The photocatalytic experiments were repeated three times to evaluate the regeneration capability and reusability of the photocatalysts. 3. Result and Discussion 3.1. High Resolution Transmission Electron Microscopy (HRTEM) The morphology and crystalline structure of TiO₂, TiO₂ NRCs, TiO₂–Ag and TiO₂–Ag NRCs were investigated using high-resolution transmission electron microscopy (HRTEM), providing deep insights into their fundamental characteristics. Figure 1 displays TEM images of the newly synthesized TiO₂ NRCs, revealing a nanorod-like morphology with diameters ranging from 20 to 30 nm and lengths between 50 and 90 nm. HRTEM images offer detailed structural information, showing the highly crystalline nature of these nanorods. Importantly, the measured lattice spacing of approximately 0.35 nm corresponds to the (110) crystal planes of rutile TiO₂, confirming the crystalline phase and structural integrity of the nanorods. These HRTEM results demonstrate that the TiO₂ NRCs were successfully synthesized via a one-step reduction technique, consistent with the phase identification obtained from XRD analysis. 3.2. X-ray diffraction analysis The X-ray diffraction (XRD) patterns of titanium dioxide nanoparticles (TiO₂ NPs), TiO₂ nanorod like composites (TiO₂ NRCs), silver-doped TiO₂ nanoparticles (TiO₂–Ag NPs), and silver-doped nanorod composites (TiO₂–Ag NRCs) synthesized via chemical reduction are presented in Fig. 2 . anatase phase confirmation Figs. 2 a and 2 b reveal that all synthesized samples exhibit diffraction peaks at 2θ values of: 25.2° (1 0 1), 37.7° (0 0 4), 48.02° (2 0 0), 53.8° (1 0 5), 55.1° (2 1 1), 62.6° (2 0 4), 68.8° (1 1 6), 70.3° (2 2 0) and 75.0° (2 1 5). These peaks correspond to the anatase phase of TiO₂, matching JCPDS card No. 21-1272, confirming successful synthesis of anatase TiO₂ in all samples. In the XRD patterns of TiO₂–Ag NRCs (Figs. 2 c and 2 d), the characteristic peaks of metallic silver at 2θ ≈ 38.7° (111) and 44.7° (200) are notably present. These peaks are typically indicative of face-centered cubic (fcc) Ag crystallites. Despite this the presence of Ag in the composites was confirmed by SAED analysis, which clearly demonstrated the formation of crystalline Ag structures. The absence of Ag peaks in XRD can be attributed to the extremely small particle size of Ag nanoparticles, which leads to peak broadening and low diffraction intensity often below the detection limit of XRD. This explanation is consistent with previous literature [ 31 – 33 ]. D = \(\:\frac{K\lambda\:}{\beta\:\text{Cos}\theta\:}\) ……………………………….. (1) In this analysis, precise measurement parameters, including the wavelength of X-rays (λ), full width at half maximum (β), the Bragg angle (θ) and the shape factor (λK), are critically important in understanding the crystalline properties of various composites. Using the strongest diffraction peak in each XRD pattern, the average crystallite sizes were calculated as TiO 2 nanoparticles, TiO 2 nanorod crystals, TiO₂–Ag nanoparticles, and TiO₂–Ag NRCs composites are determined to be 18.3, 14.5, 22.7, and 27.4 nm, respectively. The sharper diffraction peaks indicate high crystallinity and suggest a porous crystalline structure, which can significantly enhance photocatalytic performance by providing 3.3. Diffuse Reflectance Spectra The synthetic chemical reduction method produced TiO₂ nanoparticles (NPs), TiO₂ nanorod crystals (NRCs), and their corresponding TiO₂–Ag nanocomposites. Silver ions were adsorbed onto the TiO₂ surface and subsequently reduced using sodium borohydride at room temperature, without stabilizers or surfactants. This was confirmed via diffuse reflectance spectroscopy. The UV–Vis diffuse reflectance spectra of the synthesized TiO₂ and TiO₂–Ag NRCs are presented in Fig. 3 . Pure TiO₂ shows no absorption in the visible region due to its wide band gap (~ 3.2 eV). Upon silver deposition, significant absorption appears between 450 and 550 nm, corresponding to the surface plasmon resonance (SPR) of Ag nanoparticles, consistent with previous reports. TiO₂ nanoparticle films display a characteristic UV absorption band around 390 nm. Among the samples, TiO₂–Ag NRCs show a pronounced red shift, with absorption extending from 450 to 550 nm. The SPR peak position and intensity depend on Ag content, particle size, dispersion, and morphology. A weak SPR peak in the TiO₂–Ag NRCs suggests limited metallic Ag content; however, its red shift indicates larger Ag nanoparticles compared to TiO₂–Ag NPs. All TiO₂ structures retain their characteristic absorption peak, indicating no chemical alteration. Importantly, TiO₂–Ag NRCs show a significant shift of the absorption edge toward visible wavelengths, enhancing visible-light absorption. This improvement is crucial for effective photocatalytic degradation of organic dyes. 3.4. FT-IR Spectra Analysis The Fourier Transform Infrared (FT-IR) spectra of the prepared nanomaterials TiO₂ nanoparticles (NPs), TiO₂ nanorod crystals (NRCs), TiO₂–Ag nanoparticles, and TiO₂–Ag nanorod-like crystal nanocomposites are shown in Fig. 4 . The spectra were recorded over the range 400–4000 cm⁻¹. In all samples, the broad absorption band observed in the 3410–3000 cm⁻¹ region is attributed to O–H stretching vibrations, indicating the presence of adsorbed water molecules and hydroxyl groups on the surface. The absorption peaks appearing between 2940 and 1465 cm⁻¹ correspond to Ti–OH bending and stretching vibrations, which confirm the existence of surface hydroxyl groups, commonly formed during hydrolysis and annealing processes. The characteristic vibrational modes of anatase TiO₂ are evident in the 420–855 cm⁻¹ regions. The prominent bands at 640 cm⁻¹ and 551 cm⁻¹ are assigned to the bending and stretching vibrations of Ti–O–Ti bonds, respectively. These peaks strongly indicate the formation of anatase crystalline phase in both the TiO₂ nanostructures and the TiO₂–Ag composites. Overall, the FT-IR results confirm the presence of surface hydroxyl groups and the successful formation of anatase TiO₂, while also suggesting effective incorporation of Ag into the TiO₂ matrix. 3.5. Raman Spectra analysis To confirm the formation of crystalline structures and to assess the effect of silver nanoparticles (Ag NP) doping on titanium dioxide (TiO₂) nanostructures, Raman spectroscopy was performed on TiO₂ nanoparticles (NPs), TiO₂ nanorod crystals (NRCs), TiO₂–Ag NPs, and TiO₂–Ag NRCs. The resulting spectra are presented in Fig. 5 . All samples exhibited three dominant Raman peaks at approximately 427, 545, and 665 cm⁻¹, corresponding to the B₁g, B₁g A₁g, and Eg vibrational modes, respectively, and characteristic of the anatase phase of TiO₂. Importantly, the Raman spectra of TiO₂ NRCs and TiO₂–Ag NRCs showed no additional peaks indicative of secondary phases. These observations are consistent with the X-ray diffraction (XRD) results, confirming the preservation of the anatase crystal structure following Ag NP incorporation. 3.6. Photoluminescence Spectra and Electrochemical Impedance Spectroscopy The charge separation and electron–hole recombination properties of the synthesized TiO₂ NPs, TiO₂ NRCs, and TiO₂–Ag nanorod like crystals (NRCs) nanocomposites were investigated using photoluminescence (PL) spectroscopy, as presented in Fig. 6 a. PL spectroscopy is an essential technique for assessing the dynamics of charge carriers because PL emission originates from the recombination of photoexcited electrons and holes within semiconductor particles [ 41 – 44 ]. The spectra were recorded in the wavelength range of 350–500 nm. The PL intensity of TiO₂ NPs was significantly higher compared to that of TiO₂ NRCs and TiO₂–Ag NRCs, indicating that the recombination of photogenerated electron–hole pairs is more pronounced in the nanoparticle form. Conversely, the reduced PL intensity observed in TiO₂ NRCs and TiO₂–Ag nanocomposites suggests more efficient charge separation and slower recombination. In particular, the coupling of Ag with TiO₂ in the heterostructures appears to substantially suppress electron hole recombination, thereby enhancing the photocatalytic performance. To further evaluate charge transfer dynamics, electrochemical impedance spectroscopy (EIS) was employed. EIS provides valuable information on the electrical properties of modified electrodes and the interfacial charge transfer resistance in electrochemical cells. The EIS measurements for TiO₂ NRCs and TiO₂–Ag NRCs were conducted under UV illumination at their respective open-circuit potentials, as shown in Fig. 6 b. The Nyquist plots demonstrate that the semicircle diameter decreases with increasing Ag content, indicating reduced charge-transfer resistance within the composite film. This reduction facilitates faster interfacial charge transport and supports more effective separation of photogenerated electron–hole pairs. The enhanced performance of TiO₂–Ag nanocomposites can be attributed to the formation of Schottky junctions at the TiO₂/Ag interface. Electrons excited into the conduction band of TiO₂ can be transferred to Ag, which acts as an electron sink. This process prolongs the lifetime of holes remaining in TiO₂ and suppresses recombination. Thus, the observed decrease in impedance with increased Ag content is consistent with improved charge separation, aligning well with the photocurrent measurements. 3.7. Photocatalytic Degradation of Methylene Blue Using TiO₂ –Ag Nanocomposites Methylene blue (MB) is extensively used in industrial processes, yet its widespread application often results in significant environmental contamination. In this context, the photocatalytic efficiency of synthesized TiO₂–Ag nanocomposites was investigated through the degradation of MB under direct sunlight irradiation. The variation in MB absorbance over different irradiation intervals, mediated by TiO₂ nanostructures, is presented in Fig. 7 . A significant decrease in the absorption peak of MB at 661 nm was observed over time, confirming the photocatalytic decomposition of MB in the presence of TiO₂–Ag nanocomposite catalysts. This result underscores the potential of these nanocomposites in addressing dye contamination in wastewater. The degradation efficiency was expressed as C/C₀ , where C and C₀ denote the MB concentration at time t and the initial concentration, respectively. Degussa P25 was employed as a benchmark for comparison. Prior to light exposure, the MB solution containing the catalyst was stirred in the dark for 45 minutes to achieve adsorption–desorption equilibrium. The photocatalytic performances of the prepared samples TiO₂ nanoparticles (NPs), TiO₂ nanorod crystals (NRCs), TiO₂–Ag NPs, and TiO₂–Ag NRCs under sunlight irradiation are shown in Fig. 7 . As expected, the TiO₂–Ag NRCs, characterized as heterojunction composites, exhibited significantly enhanced photocatalytic activity for MB degradation. Dark adsorption measurements confirmed that adsorption–desorption equilibrium was maintained during the photocatalytic process. Among the samples tested, TiO₂–Ag NRCs demonstrated the highest photocatalytic activity, achieving an average MB degradation rate of 97.7% within 60 minutes. This exceptional performance is attributed to the improved crystallinity and strong interfacial interaction between Ag and TiO₂, which enhances charge separation. The photocatalytic activity follows the order: TiO₂–Ag NRCs > TiO₂ NRCs > TiO₂–Ag NPs and TiO₂ P25. In contrast, Degussa P25 exhibited poor photocatalytic performance, with approximately 79% of MB remaining in the solution after 60 minutes. To further evaluate the kinetics, the relationship between ln(C₀/Cₜ) and irradiation time was plotted (Fig. 8 ). The linearity of this plot confirms that the degradation process follows pseudo-first-order kinetics, and the apparent rate constant k₁ was determined using the first-order equation: ln(C 0 /C t ) = k 1t . The calculated rate constants for TiO₂ NPs, TiO₂ NRCs, TiO₂–Ag NPs, and TiO₂–Ag NRCs were 0.01564, 0.02566, 0.02986, and 0.08429, respectively. These values indicate that the TiO₂–Ag NRCs composite possesses the highest photocatalytic activity, likely due to effective separation of photogenerated electron–hole pairs (e⁻…h⁺). Additionally, the importance of core–shell geometry was highlighted by synthesizing similar composite nanostructures under identical conditions. However, the core–shell morphology resulted in unfavorable photocatalytic performance, demonstrating that the heterojunction structure of TiO₂–Ag NRCs is more effective for MB degradation. 3.8. Recycling Photocatalyst The durability and performance of heterojunction photocatalysts are critical for their practical application, especially in repeated recycling processes. In this study, the reusability of synthesized TiO₂ nanoparticles (NPs), TiO₂ nanorod crystals (NRCs), and their silver-enhanced counterparts TiO₂–Ag NPs and TiO₂–Ag NRCs was thoroughly evaluated. The photocatalysts were tested over four consecutive cycles for the degradation of methylene blue under direct sunlight, with the results presented in Fig. 9 . After each cycle, the photocatalysts were recovered by centrifugation and subsequently dried for eight hours at 80°C before being reused at the same concentration. This regeneration protocol is consistent with previously reported methods [ 49 ]. Importantly, TiO₂ NRCs and TiO₂–Ag NRCs exhibited excellent stability and sustained photocatalytic efficiency across all four cycles, highlighting their suitability for long-term environmental remediation applications. 3.9. Photocatalytic Mechanism The proposed photocatalytic reaction process under direct sunlight is illustrated in Scheme 2, highlighting the critical components and reaction pathways. Silver (Ag) significantly enhances the visible-light response of the composite by improving light absorption and altering the band-gap structure, as evidenced in Fig. 10 . Upon exposure to visible light, electrons in the TiO₂ conduction band (CB) become excited and are rapidly transferred to the Ag nanoparticles. The one-dimensional nanorod–chain (NRCs) architecture facilitates the efficient transport of these high-energy electrons from the TiO₂ CB to the surface of Ag, where they react with molecular oxygen (O₂) to form superoxide radicals (•O₂⁻). Meanwhile, the remaining photoexcited electrons within the TiO₂ conduction band further interact with dissolved O₂, producing additional •O₂⁻ species. These reactive intermediates are essential for the oxidative degradation of nearby organic pollutants, ultimately converting them into CO₂ and H₂O. This pathway highlights the pivotal role of superoxide radicals in the photocatalytic process. Additionally, the engineered one-dimensional nanostructure effectively prevents Ag nanoparticle aggregation, thereby enhancing photocatalytic stability and maintaining high catalytic efficiency throughout repeated cycles. Importantly, in the TiO₂–Ag NRCs system, holes (h⁺) are identified as the primary active species, rather than hydroxyl radicals (•OH). This finding indicates that the grafted TiO₂ serves as a conductive pathway for holes, enabling efficient separation of photogenerated electrons and holes. This enhanced charge separation is a key factor contributing to the improved photocatalytic performance of the TiO₂–Ag NRCs composite. 4. Conclusion In summary, TiO₂–Ag nanorod like crystal (NRC) composites were successfully synthesized via a reduction method, resulting in significantly enhanced photocatalytic performance under visible light compared to conventional TiO₂–Ag nanoparticles. This enhancement is primarily attributed to the optimized distribution of Ag nanoparticles within the 1D nanostructure. Within the Ag–TiO₂ heterojunction, Ag plays a dual role: it extends light absorption into the visible region and promotes rapid electron transfer, thereby effectively suppressing charge recombination, consequently, the 1D TiO₂–Ag NRC composites exhibit superior photocatalytic activities. The development of these highly efficient 1D TiO₂–Ag nanocomposites is expected to broaden the applicability of photocatalytic systems. Specifically, their use as effective photocatalysts offers a promising strategy for degrading organic pollutants such as dyes in water purification and environmental remediation. Declarations Author Contribution The surface Reactivity of Silver Nanoparticles Doped with TiO2 Nanorod like crystals for enhancing Photocatalytic Degradation of harmful water pollutants under visible - light irradiations Authors contribution:1. Authors: A, B, Synthesis of Nanomaterials and Methodology and wrote the main manuscript text. 2.Authors: C,D, prepared figures and reviewed the manuscript.3.Author: E, over all the reviewed the manuscript and corrections. Acknowledgment The author, P. Govindhan, gratefully acknowledges the staff members of the Department of Chemistry, Annapoorana Engineering College, Salem, for their support in carrying out this research work. The author also extends sincere thanks to Mr. M. Chinnadurai for his assistance with Raman, XRD, and PL spectroscopy measurements. References H.L. Hosgün, M.T. Aytekin Aydın, Synthesis, characterization and photocatalytic activity of boron-doped titanium dioxide nanotubes, J. Mole. Stru. 1180 (2019) 676–682. T. Gakhar, A. Hazra, Synthesis of go loaded TiO 2 nanotubes array by anodic oxidation for efficient detection of organic vapor J. Elect. Mate, 48, (2019) 5342–5347. A. Rajput, M. Rahman, MH Rahman A. 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Bullet., 70, (2015) 129. Y. Wen, H. Ding, Y. Shan, Preparation and visible light photocatalytic activity of Ag/TiO 2 /graphene nanocomposite,Nanoscale. 3, (2011) 4411. S. Yang, H. Wang, H. Yu, S. Zhang, Y. Fang, S. Zhang, F. Peng, A facile fabrication of hierarchical Ag nanoparticles-decorated N-TiO 2 with enhanced photocatalytic hydrogen production under solar light,Int. J. Hydrogen Energy., 41, (2016) 3446. H. Xun, Z. Zhang, A. Yu, J. Yi, Remarkably enhanced hydrogen sensing of highly- ordered SnO 2 -decorated TiO 2 nanotubes, Sensors Actuators: B. 273 (2018) 983. S. Abu Bakar, G. Byzynski, C. Ribeiro, Synergistic effect on the photocatalytic activity of N-doped TiO 2 nanorods synthesized by novel route with exposed (110) facet, J. Alloy. Comp, 666 (2016) 38. P. Govindhan, C. Pragathiswaran, M. Chinnadurai, A magnetic Fe 3 O 4 decorated TiO 2 nanoparticles application for photocatalytic degradation of methylene blue (MB) under direct sunlight irradiation, J. Mater Sci: Mater Electron. 29, (2018) 6458. P. Govindhan, C. Pragathiswaran, Synthesis and characterization of TiO 2 @SiO 2 –Ag nanocomposites towards photocatalytic degradation of rhodamine Band methylene blue, J. Mater Sci: Mater Electron, 27, (2016) 8778–8785. Schemes Schemes 1 and 2 are not available with this version. Additional Declarations No competing interests reported. Cite Share Download PDF Status: Under Revision Version 1 posted Editorial decision: Revision requested 16 Apr, 2026 Reviews received at journal 14 Apr, 2026 Reviewers agreed at journal 14 Apr, 2026 Reviews received at journal 11 Mar, 2026 Reviewers agreed at journal 06 Mar, 2026 Reviewers agreed at journal 06 Mar, 2026 Reviewers invited by journal 06 Mar, 2026 Editor assigned by journal 14 Feb, 2026 Submission checks completed at journal 10 Feb, 2026 First submitted to journal 10 Feb, 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. We do this by developing innovative software and high quality services for the global research community. Our growing team is made up of researchers and industry professionals working together to solve the most critical problems facing scientific publishing. Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-8839922","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":602581291,"identity":"734fe8b3-de15-4aba-928e-c7b43f267e39","order_by":0,"name":"P. 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NRCs\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u003c/p\u003e","description":"","filename":"image1.png","url":"https://assets-eu.researchsquare.com/files/rs-8839922/v1/46c4847edabd51b41ab65b47.png"},{"id":104425068,"identity":"c0268b4a-768f-411b-8db9-d3b78a45dba5","added_by":"auto","created_at":"2026-03-11 14:33:16","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":71854,"visible":true,"origin":"","legend":"\u003cp\u003eXRD patterns of as-prepared TiO\u003csub\u003e2\u003c/sub\u003e NCRs (a), Ag-TiO\u003csub\u003e2\u003c/sub\u003e NCRs (b), TiO\u003csub\u003e2\u003c/sub\u003e NPs (c), Ag-TiO\u003csub\u003e2\u003c/sub\u003e NPs (d).\u003c/p\u003e","description":"","filename":"image2.png","url":"https://assets-eu.researchsquare.com/files/rs-8839922/v1/0ff350d8d9581760730c9690.png"},{"id":104425070,"identity":"760927a5-a859-4606-80a4-fed9c444583a","added_by":"auto","created_at":"2026-03-11 14:33:17","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":125761,"visible":true,"origin":"","legend":"\u003cp\u003eDiffuse reflectance spectra (DRS) (a) TiO\u003csub\u003e2\u003c/sub\u003e NPs, (b) TiO\u003csub\u003e2\u003c/sub\u003e NCRs, (c) TiO\u003csub\u003e2\u003c/sub\u003e-Ag- NPs, (d) TiO\u003csub\u003e2\u003c/sub\u003e-Ag- NCRs.\u003c/p\u003e","description":"","filename":"image3.png","url":"https://assets-eu.researchsquare.com/files/rs-8839922/v1/a7d8f6594b3084a55aad7cb3.png"},{"id":104779953,"identity":"521e33d3-5582-44c8-9b90-e4ef3c301045","added_by":"auto","created_at":"2026-03-17 07:48:25","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":110870,"visible":true,"origin":"","legend":"\u003cp\u003eFT-IR spectra of as-prepared (a) TiO\u003csub\u003e2\u003c/sub\u003e NPs, (b) TiO\u003csub\u003e2\u003c/sub\u003e NCRs, (c) TiO\u003csub\u003e2\u003c/sub\u003e-Ag NPs, (d) TiO\u003csub\u003e2\u003c/sub\u003e-Ag NCRs.\u003c/p\u003e","description":"","filename":"image4.png","url":"https://assets-eu.researchsquare.com/files/rs-8839922/v1/4373b820e6de872c8024542b.png"},{"id":104425065,"identity":"4eb9895e-6581-40ea-8066-8ac36c9e150e","added_by":"auto","created_at":"2026-03-11 14:33:16","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":97696,"visible":true,"origin":"","legend":"\u003cp\u003eRaman spectra of as prepared (a) TiO\u003csub\u003e2\u003c/sub\u003e NPs, (b) TiO\u003csub\u003e2\u003c/sub\u003e NCRs, (c) TiO\u003csub\u003e2\u003c/sub\u003e-Ag NPs, (d) TiO\u003csub\u003e2\u003c/sub\u003e-Ag NCRs.\u003c/p\u003e","description":"","filename":"image5.png","url":"https://assets-eu.researchsquare.com/files/rs-8839922/v1/acb57a6a60faf7a2fb2e4d59.png"},{"id":104425069,"identity":"b14c4cad-724d-4e8a-bf8e-661242527dd1","added_by":"auto","created_at":"2026-03-11 14:33:16","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":153700,"visible":true,"origin":"","legend":"\u003cp\u003e(a) PL and (b) EI spectra of (a) TiO\u003csub\u003e2\u003c/sub\u003e NPs, (b) TiO\u003csub\u003e2\u003c/sub\u003e NCRs, (c) TiO\u003csub\u003e2\u003c/sub\u003e-Ag NPs (d) TiO\u003csub\u003e2\u003c/sub\u003e-Ag NCRs.\u003c/p\u003e","description":"","filename":"image6.png","url":"https://assets-eu.researchsquare.com/files/rs-8839922/v1/3c3dc230beed8df2533b5fba.png"},{"id":104425066,"identity":"9b2b3f20-bad6-41e1-8058-ccf493e8e819","added_by":"auto","created_at":"2026-03-11 14:33:16","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":433543,"visible":true,"origin":"","legend":"\u003cp\u003eThe absorption spectra of MB recorded at different time intervals during sun light \u0026nbsp;irradiation in the presence of TiO\u003csub\u003e2\u003c/sub\u003e nanostructures, (a) TiO\u003csub\u003e2\u003c/sub\u003e NPs, (b) TiO\u003csub\u003e2\u003c/sub\u003e NRCs, \u0026nbsp;(c) TiO\u003csub\u003e2\u003c/sub\u003e-Ag-NPs, (d) TiO\u003csub\u003e2\u003c/sub\u003e-Ag-NRCs.\u003c/p\u003e","description":"","filename":"image7.png","url":"https://assets-eu.researchsquare.com/files/rs-8839922/v1/4023e3532dfa9bef294e9935.png"},{"id":104780162,"identity":"8a79108c-2b5b-4da2-a80f-3e4a02fd3698","added_by":"auto","created_at":"2026-03-17 07:51:08","extension":"jpeg","order_by":8,"title":"Figure 8","display":"","copyAsset":false,"role":"figure","size":83878,"visible":true,"origin":"","legend":"\u003cp\u003e(a) Photocatalytic degradation of methylene blue (MB) in the presence of different catalysts under sunlight irradiation, (b) ln (C\u003csub\u003e0\u003c/sub\u003e/C\u003csub\u003et\u003c/sub\u003e) Vs time plots for the photocatalytic degradation of MB over synthesized composites.\u003c/p\u003e","description":"","filename":"image8.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-8839922/v1/40f61e73071946f709f5ca09.jpeg"},{"id":104425071,"identity":"bc8f0599-33b7-49c2-afec-4e95c7b6fc91","added_by":"auto","created_at":"2026-03-11 14:33:17","extension":"png","order_by":9,"title":"Figure 9","display":"","copyAsset":false,"role":"figure","size":42103,"visible":true,"origin":"","legend":"\u003cp\u003eRecycle process of photocatalytic dye degradation (a) TiO\u003csub\u003e2\u003c/sub\u003e NPs, (b) TiO\u003csub\u003e2\u003c/sub\u003e NRCs, (c) TiO\u003csub\u003e2\u003c/sub\u003e-Ag NPs, (d) TiO\u003csub\u003e2\u003c/sub\u003e-Ag NRCs\u003c/p\u003e","description":"","filename":"image9.png","url":"https://assets-eu.researchsquare.com/files/rs-8839922/v1/747b349acb8e2751cf04f3ac.png"},{"id":104425073,"identity":"142f4163-e3ef-4821-9fd5-915b0ff44e39","added_by":"auto","created_at":"2026-03-11 14:33:17","extension":"png","order_by":10,"title":"Figure 10","display":"","copyAsset":false,"role":"figure","size":2758701,"visible":true,"origin":"","legend":"\u003cp\u003eSchematic representation of the possible photocatalytic mechanism of Ag-TiO\u003csub\u003e2\u003c/sub\u003e NRCs\u0026nbsp; nanocomposites under sunlight.\u003c/p\u003e","description":"","filename":"image10.png","url":"https://assets-eu.researchsquare.com/files/rs-8839922/v1/7c6cb074efb57a043726b199.png"},{"id":104784230,"identity":"0660bfb3-de81-4659-a0da-2a117aeb3815","added_by":"auto","created_at":"2026-03-17 08:05:57","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":7562465,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-8839922/v1/960aec96-9a95-4c37-a516-3982b8ce34cb.pdf"}],"financialInterests":"No competing interests reported.","formattedTitle":"The surface Reactivity of Silver Nanoparticles Doped with TiO 2 Nanorod like crystals for enhancing Photocatalytic Degradation of harmful water pollutants under visible - light irradiations","fulltext":[{"header":"1. Introduction","content":"\u003cp\u003eOver the past decades, titanium dioxide (TiO₂) has attracted significant attention due to its wide range of applications in photocatalysis, water purification, sensor technology, and dye-sensitized solar cells, owing to its chemical stability, low toxicity, and cost-effectiveness [\u003cspan additionalcitationids=\"CR2\" citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e]. TiO₂ possesses a wide band gap of approximately 3.0 eV for the rutile phase and 3.2 eV for the anatase phase, enabling efficient excitation of electrons from the valence band to the conduction band under ultraviolet irradiation. The growing dependence on photocatalysts and solar-energy-driven technologies has highlighted advanced oxidation processes as promising alternatives for environmental remediation, underscoring the importance of developing sustainable and efficient materials [\u003cspan additionalcitationids=\"CR5\" citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e]. TiO₂ nanoparticles exist in three distinct crystalline phases: anatase, brookite, and rutile. Among these, the rutile phase is thermodynamically more stable, whereas anatase and brookite are metastable. Phase transformations between these structures are influenced by several factors, including particle size, pH, surface area, and solution composition [\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e, \u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eTiO₂ is regarded as a novel and versatile material due to its high adsorption capacity, which enhances dye molecule uptake. However, increasing the dopant concentration beyond an optimal level can lead to the formation of secondary phases, resulting in reduced visible-light absorption due to increased electron\u0026ndash;hole recombination [\u003cspan additionalcitationids=\"CR10 CR11 CR12 CR13\" citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e]. Surface morphology modifications induced by metal doping (e.g., Au, Ag, and Pt) in TiO₂ nanostructures such as nanoparticles, nanotubes, nanorods, and nanospheres have been shown to broaden visible-light absorption and significantly enhance photocatalytic activity. Among these structures, TiO₂ nanotubes exhibit superior photocatalytic performance compared to TiO₂ nanoparticles, attributed to their higher specific surface area and improved crystalline order. Furthermore, the deposition of silver nanoparticles on TiO₂ surfaces markedly enhances photocatalytic degradation rates through localized surface plasmon resonance effects and efficient charge separation at the Ag/TiO₂ interface [\u003cspan additionalcitationids=\"CR16 CR17 CR18\" citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e]. Ag/TiO₂ composite materials have been extensively studied for photocatalytic applications and also demonstrate considerable potential in heterogeneous catalysis, dye-sensitized solar cells, photovoltaic devices, sensors, adsorption processes, and surface coatings due to their favorable surface morphology and electronic properties [\u003cspan additionalcitationids=\"CR21\" citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eIn addition, surface modification of TiO₂ into low-dimensional nanostructures (1D and 2D) improves photoelectric conversion efficiency through enhanced light harvesting, multilevel scattering, and accelerated electron transport. Recent studies have further expanded TiO₂ functionality by integrating it with materials such as polymers, graphene oxide, and carbon nanotubes [\u003cspan additionalcitationids=\"CR24\" citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e]. The catalytic activity of TiO₂-based composites is particularly significant in immobilization strategies involving oxide heterostructures, including TiO₂@Fe₃O₄ [\u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e], TiO₂@SiO₂ [\u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e], ZnO@TiO₂ [\u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e], and TiO₂@Fe₃O₄@SiO₂. These composite systems exhibit improved charge separation and enhanced photocatalytic performance, particularly under visible-light irradiation. In this study, TiO₂ nanoparticles were synthesized via a sol\u0026ndash;gel method and subsequently modified to form silver-decorated TiO₂ nanocrystal composites (Ag\u0026ndash;TiO₂ NRCs). The photocatalytic efficiency of these materials was evaluated through the degradation of methylene blue dye under sunlight irradiation, demonstrating their significant potential for environmental remediation applications.\u003c/p\u003e"},{"header":"2. Experimental methods:","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003e2.1. Materials:\u003c/h2\u003e \u003cp\u003eTitanium(IV) chloride, titanium isopropoxide (TTIP), ammonium hydroxide (NH₄OH), sodium hydroxide (NaOH), hydrochloric acid (HCl), perchloric acid (HClO₄), ethylene glycol (EG), and polyvinylpyrrolidone (PVP) were procured from Merck Chemicals and used as precursor materials for the synthesis of various titanium dioxide nanostructures, including nanoparticles, nanospheres, and nanorods. Silver nitrate (AgNO₃, 99.9% purity), obtained from Sigma-Aldrich, and was employed as the precursor for the synthesis of silver nanoparticles. All chemicals were of analytical grade and were used without further purification. Double-distilled water was used throughout the experiments for the preparation of aqueous solutions and for washing processes unless otherwise specified.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec4\" class=\"Section2\"\u003e \u003ch2\u003e2.2. Synthesis of TiO\u003csub\u003e2\u003c/sub\u003e Nanorod Crystals (TiO\u003csub\u003e2\u003c/sub\u003e NRCs)\u003c/h2\u003e \u003cp\u003eThe synthesized TiO₂ nanoparticles were prepared according to our previous work [\u003cspan citationid=\"CR54\" class=\"CitationRef\"\u003e54\u003c/span\u003e]. TiO₂ nanorod-like crystals (TiO₂ NRCs) were synthesized using a carefully controlled procedure emphasizing precision and proper handling of chemical materials. Initially, 20 mL of 2 N mixed hydroxide solution, composed of NaOH and KOH in an equal ratio, was transferred into a 50 mL Teflon-lined vessel and sealed with a cover to prevent dust contamination. Subsequently, 1 g of the synthesized TiO₂ nanoparticles was gently placed onto the hydroxide solution inside the vessel. The sealed vessel was then heated in a furnace at 200\u0026deg;C for 3 h. During this stage, the vessel was periodically agitated to ensure uniform mixing of the reactants. Afterward, the sample was returned to the furnace and maintained at 200\u0026deg;C for an additional 36 h to facilitate further crystal growth and chemical interaction. Upon completion of the heating process, the product was washed repeatedly with 0.1 M HCl solution followed by distilled water until a neutral pH (\u0026asymp;\u0026thinsp;7.0) was achieved. Finally, the obtained material was calcined at various temperatures to stabilize and enhance the crystalline structure. For comparison, an additional sample was prepared following the same synthesis protocol but washed exclusively with distilled water. This comparison highlights the influence of the washing process on the structural and physicochemical properties of the resulting TiO₂ NRCs.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec5\" class=\"Section2\"\u003e \u003ch2\u003e\u003cb\u003e2.3. Synthesis of TiO₂ \u0026ndash;Ag Nanorod Crystals (NRCs)\u003c/b\u003e\u003c/h2\u003e \u003cp\u003eSilver nanoparticles were deposited onto TiO₂ nanorod-like crystals (NRCs) via a chemical reduction method, in which Ag⁺ ions were reduced to metallic Ag nanoparticles. Briefly, 1 g of pre-synthesized TiO₂ NRCs was dispersed in 250 mL of double-distilled water and stirred continuously for 30 min to achieve a homogeneous suspension. Subsequently, Ag⁺ ions (4 wt%) were added under constant stirring. The reduction of Ag⁺ was carried out by the dropwise addition of NaBH₄ until a greenish-yellow coloration appeared, indicating the formation of TiO₂\u0026ndash;Ag NRC nanocomposites. The reaction mixture was further stirred for 30 min to ensure complete reduction and uniform deposition of Ag nanoparticles. The resulting nanocomposites were collected by filtration, thoroughly washed with double-distilled water, and dried at 60\u0026deg;C for 3 h. Finally, the dried samples were calcined at 450\u0026deg;C for 3 h to obtain the TiO₂\u0026ndash;Ag NRC nanocomposites (Scheme 1).\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec6\" class=\"Section2\"\u003e \u003ch2\u003e2.4. Characterization Studies\u003c/h2\u003e \u003cp\u003eThe optical absorption properties of various TiO₂ nanostructures and TiO₂\u0026ndash;Ag ₂ NRC catalysts were investigated using a UV\u0026ndash;vis spectrophotometer (Shimadzu UV-2550). Diffuse reflectance spectra (DRS) of pristine TiO₂ nanoparticle powders and TiO₂\u0026ndash;Ag NRC nanocomposites were recorded using an ISR-2200 DRS accessory attached to the same instrument. Powder X-ray diffraction (XRD) patterns were obtained using a Scintag XDS-2000 diffractometer with Cu Kα radiation (λ\u0026thinsp;=\u0026thinsp;1.5406 \u0026Aring;), operated at 40 kV and 30 mA. The morphology and particle size of the nanomaterials were examined by high-resolution transmission electron microscopy (HRTEM). SEM images were acquired using a TESCAN VEGA3 microscope, while TEM images were recorded on an FEI transmission electron microscope operating at an accelerating voltage of 200 kV. Raman spectra were collected in the range of 300\u0026ndash;1000 cm⁻\u0026sup1; using a JASCO-3100 laser Raman spectrometer. Photoluminescence (PL) spectra were measured using a Fluoromax-4 spectrofluorometer with an excitation wavelength of 325 nm to evaluate the charge carrier recombination behavior and photocatalytic performance of the TiO₂\u0026ndash;Ag NRC nanocomposites. Electrochemical impedance spectroscopy (EIS) measurements were carried out using a potentiostat (model EIS-650) to analyze charge transfer characteristics. Fourier transform infrared (FTIR) spectra were recorded using a Shimadzu FT-IR-650 spectrometer in the KBr pellet mode to identify the functional groups present in the TiO₂\u0026ndash;Ag NRC nanocomposites.\u003c/p\u003e \u003c/div\u003e\n\u003ch3\u003e2.5. Photocatalytic activity measurement\u003c/h3\u003e\n\u003cp\u003eThe photocatalytic performance of silver-decorated TiO₂ nanoparticles (TiO₂ NPs), TiO₂ nanorod clusters (TiO₂ NRCs), TiO₂\u0026ndash;Ag NPs, and TiO₂\u0026ndash;Ag NRCs was evaluated via the degradation of methylene blue (MB) dye under natural sunlight irradiation. To ensure experimental accuracy, the reaction vessel was placed inside a sealed black box equipped with a top opening to allow controlled exposure to visible light. For each experiment, 0.05 g of the photocatalyst was dispersed in 100 mL of methylene blue solution with a concentration of 1.05 g L⁻\u0026sup1;. The suspension was first ultrasonicated for 5 min to achieve uniform dispersion, followed by magnetic stirring in the dark for 30 min to establish adsorption\u0026ndash;desorption equilibrium between the dye molecules and the photocatalyst surface. Afterward, the reaction mixture was exposed to direct sunlight during daytime hours (11:00 am 2:00 pm), corresponding to the period of maximum solar intensity. At predetermined time intervals, aliquots were withdrawn, and the residual dye concentration was analyzed using a UV\u0026ndash;Vis spectrophotometer. The photocatalytic experiments were repeated three times to evaluate the regeneration capability and reusability of the photocatalysts.\u003c/p\u003e"},{"header":"3. Result and Discussion","content":"\u003cdiv id=\"Sec9\" class=\"Section2\"\u003e \u003ch2\u003e3.1. High Resolution Transmission Electron Microscopy (HRTEM)\u003c/h2\u003e \u003cp\u003eThe morphology and crystalline structure of TiO₂, TiO₂ NRCs, TiO₂\u0026ndash;Ag and TiO₂\u0026ndash;Ag NRCs were investigated using high-resolution transmission electron microscopy (HRTEM), providing deep insights into their fundamental characteristics. Figure\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e displays TEM images of the newly synthesized TiO₂ NRCs, revealing a nanorod-like morphology with diameters ranging from 20 to 30 nm and lengths between 50 and 90 nm. HRTEM images offer detailed structural information, showing the highly crystalline nature of these nanorods. Importantly, the measured lattice spacing of approximately 0.35 nm corresponds to the (110) crystal planes of rutile TiO₂, confirming the crystalline phase and structural integrity of the nanorods. These HRTEM results demonstrate that the TiO₂ NRCs were successfully synthesized via a one-step reduction technique, consistent with the phase identification obtained from XRD analysis.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec10\" class=\"Section2\"\u003e \u003ch2\u003e3.2. X-ray diffraction analysis\u003c/h2\u003e \u003cp\u003eThe X-ray diffraction (XRD) patterns of titanium dioxide nanoparticles (TiO₂ NPs), TiO₂ nanorod like composites (TiO₂ NRCs), silver-doped TiO₂ nanoparticles (TiO₂\u0026ndash;Ag NPs), and silver-doped nanorod composites (TiO₂\u0026ndash;Ag NRCs) synthesized via chemical reduction are presented in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e. anatase phase confirmation Figs.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ea and \u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eb reveal that all synthesized samples exhibit diffraction peaks at 2θ values of: 25.2\u0026deg; (1 0 1), 37.7\u0026deg; (0 0 4), 48.02\u0026deg; (2 0 0), 53.8\u0026deg; (1 0 5), 55.1\u0026deg; (2 1 1), 62.6\u0026deg; (2 0 4), 68.8\u0026deg; (1 1 6), 70.3\u0026deg; (2 2 0) and 75.0\u0026deg; (2 1 5). These peaks correspond to the anatase phase of TiO₂, matching JCPDS card No. 21-1272, confirming successful synthesis of anatase TiO₂ in all samples. In the XRD patterns of TiO₂\u0026ndash;Ag NRCs (Figs.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ec and \u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ed), the characteristic peaks of metallic silver at 2θ\u0026thinsp;\u0026asymp;\u0026thinsp;38.7\u0026deg; (111) and 44.7\u0026deg; (200) are notably present. These peaks are typically indicative of face-centered cubic (fcc) Ag crystallites. Despite this the presence of Ag in the composites was confirmed by SAED analysis, which clearly demonstrated the formation of crystalline Ag structures. The absence of Ag peaks in XRD can be attributed to the extremely small particle size of Ag nanoparticles, which leads to peak broadening and low diffraction intensity often below the detection limit of XRD. This explanation is consistent with previous literature [\u003cspan additionalcitationids=\"CR32\" citationid=\"CR31\" class=\"CitationRef\"\u003e31\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e].\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eD = \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:\\frac{K\\lambda\\:}{\\beta\\:\\text{Cos}\\theta\\:}\\)\u003c/span\u003e\u003c/span\u003e \u0026hellip;\u0026hellip;\u0026hellip;\u0026hellip;\u0026hellip;\u0026hellip;\u0026hellip;\u0026hellip;\u0026hellip;\u0026hellip;\u0026hellip;\u0026hellip;.. (1)\u003c/p\u003e \u003cp\u003eIn this analysis, precise measurement parameters, including the wavelength of X-rays (λ), full width at half maximum (β), the Bragg angle (θ) and the shape factor (λK), are critically important in understanding the crystalline properties of various composites. Using the strongest diffraction peak in each XRD pattern, the average crystallite sizes were calculated as TiO\u003csub\u003e2\u003c/sub\u003e nanoparticles, TiO\u003csub\u003e2\u003c/sub\u003e nanorod crystals, TiO₂\u0026ndash;Ag nanoparticles, and TiO₂\u0026ndash;Ag NRCs composites are determined to be 18.3, 14.5, 22.7, and 27.4 nm, respectively. The sharper diffraction peaks indicate high crystallinity and suggest a porous crystalline structure, which can significantly enhance photocatalytic performance by providing\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec11\" class=\"Section2\"\u003e \u003ch2\u003e3.3. Diffuse Reflectance Spectra\u003c/h2\u003e \u003cp\u003eThe synthetic chemical reduction method produced TiO₂ nanoparticles (NPs), TiO₂ nanorod crystals (NRCs), and their corresponding TiO₂\u0026ndash;Ag nanocomposites. Silver ions were adsorbed onto the TiO₂ surface and subsequently reduced using sodium borohydride at room temperature, without stabilizers or surfactants. This was confirmed via diffuse reflectance spectroscopy. The UV\u0026ndash;Vis diffuse reflectance spectra of the synthesized TiO₂ and TiO₂\u0026ndash;Ag NRCs are presented in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e. Pure TiO₂ shows no absorption in the visible region due to its wide band gap (~\u0026thinsp;3.2 eV). Upon silver deposition, significant absorption appears between 450 and 550 nm, corresponding to the surface plasmon resonance (SPR) of Ag nanoparticles, consistent with previous reports. TiO₂ nanoparticle films display a characteristic UV absorption band around 390 nm. Among the samples, TiO₂\u0026ndash;Ag NRCs show a pronounced red shift, with absorption extending from 450 to 550 nm.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe SPR peak position and intensity depend on Ag content, particle size, dispersion, and morphology. A weak SPR peak in the TiO₂\u0026ndash;Ag NRCs suggests limited metallic Ag content; however, its red shift indicates larger Ag nanoparticles compared to TiO₂\u0026ndash;Ag NPs. All TiO₂ structures retain their characteristic absorption peak, indicating no chemical alteration. Importantly, TiO₂\u0026ndash;Ag NRCs show a significant shift of the absorption edge toward visible wavelengths, enhancing visible-light absorption. This improvement is crucial for effective photocatalytic degradation of organic dyes.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec12\" class=\"Section2\"\u003e \u003ch2\u003e3.4. FT-IR Spectra Analysis\u003c/h2\u003e \u003cp\u003eThe Fourier Transform Infrared (FT-IR) spectra of the prepared nanomaterials TiO₂ nanoparticles (NPs), TiO₂ nanorod crystals (NRCs), TiO₂\u0026ndash;Ag nanoparticles, and TiO₂\u0026ndash;Ag nanorod-like crystal nanocomposites are shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e. The spectra were recorded over the range 400\u0026ndash;4000 cm⁻\u0026sup1;. In all samples, the broad absorption band observed in the 3410\u0026ndash;3000 cm⁻\u0026sup1; region is attributed to O\u0026ndash;H stretching vibrations, indicating the presence of adsorbed water molecules and hydroxyl groups on the surface. The absorption peaks appearing between 2940 and 1465 cm⁻\u0026sup1; correspond to Ti\u0026ndash;OH bending and stretching vibrations, which confirm the existence of surface hydroxyl groups, commonly formed during hydrolysis and annealing processes. The characteristic vibrational modes of anatase TiO₂ are evident in the 420\u0026ndash;855 cm⁻\u0026sup1; regions. The prominent bands at 640 cm⁻\u0026sup1; and 551 cm⁻\u0026sup1; are assigned to the bending and stretching vibrations of Ti\u0026ndash;O\u0026ndash;Ti bonds, respectively. These peaks strongly indicate the formation of anatase crystalline phase in both the TiO₂ nanostructures and the TiO₂\u0026ndash;Ag composites. Overall, the FT-IR results confirm the presence of surface hydroxyl groups and the successful formation of anatase TiO₂, while also suggesting effective incorporation of Ag into the TiO₂ matrix.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec13\" class=\"Section2\"\u003e \u003ch2\u003e3.5. Raman Spectra analysis\u003c/h2\u003e \u003cp\u003eTo confirm the formation of crystalline structures and to assess the effect of silver nanoparticles (Ag NP) doping on titanium dioxide (TiO₂) nanostructures, Raman spectroscopy was performed on TiO₂ nanoparticles (NPs), TiO₂ nanorod crystals (NRCs), TiO₂\u0026ndash;Ag NPs, and TiO₂\u0026ndash;Ag NRCs. The resulting spectra are presented in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e. All samples exhibited three dominant Raman peaks at approximately 427, 545, and 665 cm⁻\u0026sup1;, corresponding to the B₁g, B₁g A₁g, and Eg vibrational modes, respectively, and characteristic of the anatase phase of TiO₂. Importantly, the Raman spectra of TiO₂ NRCs and TiO₂\u0026ndash;Ag NRCs showed no additional peaks indicative of secondary phases. These observations are consistent with the X-ray diffraction (XRD) results, confirming the preservation of the anatase crystal structure following Ag NP incorporation.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec14\" class=\"Section2\"\u003e \u003ch2\u003e3.6. Photoluminescence Spectra and Electrochemical Impedance Spectroscopy\u003c/h2\u003e \u003cp\u003eThe charge separation and electron\u0026ndash;hole recombination properties of the synthesized TiO₂ NPs, TiO₂ NRCs, and TiO₂\u0026ndash;Ag nanorod like crystals (NRCs) nanocomposites were investigated using photoluminescence (PL) spectroscopy, as presented in Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ea. PL spectroscopy is an essential technique for assessing the dynamics of charge carriers because PL emission originates from the recombination of photoexcited electrons and holes within semiconductor particles [\u003cspan additionalcitationids=\"CR42 CR43\" citationid=\"CR41\" class=\"CitationRef\"\u003e41\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR44\" class=\"CitationRef\"\u003e44\u003c/span\u003e]. The spectra were recorded in the wavelength range of 350\u0026ndash;500 nm. The PL intensity of TiO₂ NPs was significantly higher compared to that of TiO₂ NRCs and TiO₂\u0026ndash;Ag NRCs, indicating that the recombination of photogenerated electron\u0026ndash;hole pairs is more pronounced in the nanoparticle form. Conversely, the reduced PL intensity observed in TiO₂ NRCs and TiO₂\u0026ndash;Ag nanocomposites suggests more efficient charge separation and slower recombination. In particular, the coupling of Ag with TiO₂ in the heterostructures appears to substantially suppress electron hole recombination, thereby enhancing the photocatalytic performance.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eTo further evaluate charge transfer dynamics, electrochemical impedance spectroscopy (EIS) was employed. EIS provides valuable information on the electrical properties of modified electrodes and the interfacial charge transfer resistance in electrochemical cells. The EIS measurements for TiO₂ NRCs and TiO₂\u0026ndash;Ag NRCs were conducted under UV illumination at their respective open-circuit potentials, as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003eb. The Nyquist plots demonstrate that the semicircle diameter decreases with increasing Ag content, indicating reduced charge-transfer resistance within the composite film. This reduction facilitates faster interfacial charge transport and supports more effective separation of photogenerated electron\u0026ndash;hole pairs.\u003c/p\u003e \u003cp\u003eThe enhanced performance of TiO₂\u0026ndash;Ag nanocomposites can be attributed to the formation of Schottky junctions at the TiO₂/Ag interface. Electrons excited into the conduction band of TiO₂ can be transferred to Ag, which acts as an electron sink. This process prolongs the lifetime of holes remaining in TiO₂ and suppresses recombination. Thus, the observed decrease in impedance with increased Ag content is consistent with improved charge separation, aligning well with the photocurrent measurements.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec15\" class=\"Section2\"\u003e \u003ch2\u003e\u003cb\u003e3.7. Photocatalytic Degradation of Methylene Blue Using TiO₂ \u0026ndash;Ag Nanocomposites\u003c/b\u003e\u003c/h2\u003e \u003cp\u003eMethylene blue (MB) is extensively used in industrial processes, yet its widespread application often results in significant environmental contamination. In this context, the photocatalytic efficiency of synthesized TiO₂\u0026ndash;Ag nanocomposites was investigated through the degradation of MB under direct sunlight irradiation. The variation in MB absorbance over different irradiation intervals, mediated by TiO₂ nanostructures, is presented in Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003e. A significant decrease in the absorption peak of MB at 661 nm was observed over time, confirming the photocatalytic decomposition of MB in the presence of TiO₂\u0026ndash;Ag nanocomposite catalysts. This result underscores the potential of these nanocomposites in addressing dye contamination in wastewater. The degradation efficiency was expressed as \u003cb\u003eC/C₀\u003c/b\u003e, where \u003cem\u003eC\u003c/em\u003e and \u003cem\u003eC₀\u003c/em\u003e denote the MB concentration at time \u003cem\u003et\u003c/em\u003e and the initial concentration, respectively. Degussa P25 was employed as a benchmark for comparison. Prior to light exposure, the MB solution containing the catalyst was stirred in the dark for 45 minutes to achieve adsorption\u0026ndash;desorption equilibrium. The photocatalytic performances of the prepared samples TiO₂ nanoparticles (NPs), TiO₂ nanorod crystals (NRCs), TiO₂\u0026ndash;Ag NPs, and TiO₂\u0026ndash;Ag NRCs under sunlight irradiation are shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003e. As expected, the TiO₂\u0026ndash;Ag NRCs, characterized as heterojunction composites, exhibited significantly enhanced photocatalytic activity for MB degradation. Dark adsorption measurements confirmed that adsorption\u0026ndash;desorption equilibrium was maintained during the photocatalytic process. Among the samples tested, TiO₂\u0026ndash;Ag NRCs demonstrated the highest photocatalytic activity, achieving an average MB degradation rate of 97.7% within 60 minutes. This exceptional performance is attributed to the improved crystallinity and strong interfacial interaction between Ag and TiO₂, which enhances charge separation. The photocatalytic activity follows the order: TiO₂\u0026ndash;Ag NRCs\u0026thinsp;\u0026gt;\u0026thinsp;TiO₂ NRCs\u0026thinsp;\u0026gt;\u0026thinsp;TiO₂\u0026ndash;Ag NPs and TiO₂ P25. In contrast, Degussa P25 exhibited poor photocatalytic performance, with approximately 79% of MB remaining in the solution after 60 minutes. To further evaluate the kinetics, the relationship between ln(C₀/Cₜ) and irradiation time was plotted (Fig.\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e8\u003c/span\u003e). The linearity of this plot confirms that the degradation process follows pseudo-first-order kinetics, and the apparent rate constant k₁ was determined using the first-order equation: ln(C\u003csub\u003e0\u003c/sub\u003e/C\u003csub\u003et\u003c/sub\u003e) = k\u003csub\u003e1t\u003c/sub\u003e. The calculated rate constants for TiO₂ NPs, TiO₂ NRCs, TiO₂\u0026ndash;Ag NPs, and TiO₂\u0026ndash;Ag NRCs were 0.01564, 0.02566, 0.02986, and 0.08429, respectively. These values indicate that the TiO₂\u0026ndash;Ag NRCs composite possesses the highest photocatalytic activity, likely due to effective separation of photogenerated electron\u0026ndash;hole pairs (e⁻\u0026hellip;h⁺). Additionally, the importance of core\u0026ndash;shell geometry was highlighted by synthesizing similar composite nanostructures under identical conditions. However, the core\u0026ndash;shell morphology resulted in unfavorable photocatalytic performance, demonstrating that the heterojunction structure of TiO₂\u0026ndash;Ag NRCs is more effective for MB degradation.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec16\" class=\"Section2\"\u003e \u003ch2\u003e3.8. Recycling Photocatalyst\u003c/h2\u003e \u003cp\u003eThe durability and performance of heterojunction photocatalysts are critical for their practical application, especially in repeated recycling processes. In this study, the reusability of synthesized TiO₂ nanoparticles (NPs), TiO₂ nanorod crystals (NRCs), and their silver-enhanced counterparts TiO₂\u0026ndash;Ag NPs and TiO₂\u0026ndash;Ag NRCs was thoroughly evaluated. The photocatalysts were tested over four consecutive cycles for the degradation of methylene blue under direct sunlight, with the results presented in Fig.\u0026nbsp;\u003cspan refid=\"Fig9\" class=\"InternalRef\"\u003e9\u003c/span\u003e. After each cycle, the photocatalysts were recovered by centrifugation and subsequently dried for eight hours at 80\u0026deg;C before being reused at the same concentration. This regeneration protocol is consistent with previously reported methods [\u003cspan citationid=\"CR49\" class=\"CitationRef\"\u003e49\u003c/span\u003e]. Importantly, TiO₂ NRCs and TiO₂\u0026ndash;Ag NRCs exhibited excellent stability and sustained photocatalytic efficiency across all four cycles, highlighting their suitability for long-term environmental remediation applications.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec17\" class=\"Section2\"\u003e \u003ch2\u003e3.9. Photocatalytic Mechanism\u003c/h2\u003e \u003cp\u003eThe proposed photocatalytic reaction process under direct sunlight is illustrated in Scheme 2, highlighting the critical components and reaction pathways. Silver (Ag) significantly enhances the visible-light response of the composite by improving light absorption and altering the band-gap structure, as evidenced in Fig.\u0026nbsp;\u003cspan refid=\"Fig10\" class=\"InternalRef\"\u003e10\u003c/span\u003e. Upon exposure to visible light, electrons in the TiO₂ conduction band (CB) become excited and are rapidly transferred to the Ag nanoparticles. The one-dimensional nanorod\u0026ndash;chain (NRCs) architecture facilitates the efficient transport of these high-energy electrons from the TiO₂ CB to the surface of Ag, where they react with molecular oxygen (O₂) to form superoxide radicals (\u0026bull;O₂⁻). Meanwhile, the remaining photoexcited electrons within the TiO₂ conduction band further interact with dissolved O₂, producing additional \u0026bull;O₂⁻ species. These reactive intermediates are essential for the oxidative degradation of nearby organic pollutants, ultimately converting them into CO₂ and H₂O. This pathway highlights the pivotal role of superoxide radicals in the photocatalytic process. Additionally, the engineered one-dimensional nanostructure effectively prevents Ag nanoparticle aggregation, thereby enhancing photocatalytic stability and maintaining high catalytic efficiency throughout repeated cycles. Importantly, in the TiO₂\u0026ndash;Ag NRCs system, holes (h⁺) are identified as the primary active species, rather than hydroxyl radicals (\u0026bull;OH). This finding indicates that the grafted TiO₂ serves as a conductive pathway for holes, enabling efficient separation of photogenerated electrons and holes. This enhanced charge separation is a key factor contributing to the improved photocatalytic performance of the TiO₂\u0026ndash;Ag NRCs composite.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e"},{"header":"4. Conclusion","content":"\u003cp\u003eIn summary, TiO₂\u0026ndash;Ag nanorod like crystal (NRC) composites were successfully synthesized via a reduction method, resulting in significantly enhanced photocatalytic performance under visible light compared to conventional TiO₂\u0026ndash;Ag nanoparticles. This enhancement is primarily attributed to the optimized distribution of Ag nanoparticles within the 1D nanostructure. Within the Ag\u0026ndash;TiO₂ heterojunction, Ag plays a dual role: it extends light absorption into the visible region and promotes rapid electron transfer, thereby effectively suppressing charge recombination, consequently, the 1D TiO₂\u0026ndash;Ag NRC composites exhibit superior photocatalytic activities. The development of these highly efficient 1D TiO₂\u0026ndash;Ag nanocomposites is expected to broaden the applicability of photocatalytic systems. Specifically, their use as effective photocatalysts offers a promising strategy for degrading organic pollutants such as dyes in water purification and environmental remediation.\u003c/p\u003e"},{"header":"Declarations","content":"\u003ch2\u003eAuthor Contribution\u003c/h2\u003e\u003cp\u003eThe surface Reactivity of Silver Nanoparticles Doped with TiO2 Nanorod like crystals for enhancing Photocatalytic Degradation of harmful water pollutants under visible - light irradiations Authors contribution:1. Authors: A, B, Synthesis of Nanomaterials and Methodology and wrote the main manuscript text. 2.Authors: C,D, prepared figures and reviewed the manuscript.3.Author: E, over all the reviewed the manuscript and corrections.\u003c/p\u003e\u003ch2\u003eAcknowledgment\u003c/h2\u003e \u003cp\u003eThe author, P. Govindhan, gratefully acknowledges the staff members of the Department of Chemistry, Annapoorana Engineering College, Salem, for their support in carrying out this research work. The author also extends sincere thanks to Mr. M. Chinnadurai for his assistance with Raman, XRD, and PL spectroscopy measurements.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eH.L. Hosg\u0026uuml;n, M.T. Aytekin Aydın, Synthesis, characterization and photocatalytic activity of boron-doped titanium dioxide nanotubes, J. Mole. Stru. 1180 (2019) 676\u0026ndash;682.\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eT. Gakhar, A. 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Mater Sci: Mater Electron, 27, (2016) 8778\u0026ndash;8785.\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"},{"header":"Schemes","content":"\u003cp\u003eSchemes 1 and 2 are not available with this version.\u003c/p\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-nanoparticle-research","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"nano","sideBox":"Learn more about [Journal of Nanoparticle Research](http://link.springer.com/journal/11051)","snPcode":"11051","submissionUrl":"https://submission.nature.com/new-submission/11051/3","title":"Journal of Nanoparticle Research","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"TiO2 NPs, Ag-TiO2 NRCs nanocomposite, Photocatalyst, Dye degradation, Methylene Blue","lastPublishedDoi":"10.21203/rs.3.rs-8839922/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-8839922/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eA novel photocatalyst was developed through the synthesis of TiO₂ nanoparticles followed by their transformation into TiO₂ nanorod-like crystals via a hydrothermal method. The surface properties of this TiO₂ nanorod like crystals (TiO₂ NRCs) were further enhanced by decorating them with Ag nanoparticles using a chemical reduction approach, resulting in a significant improvement in photocatalytic performance of TiO₂\u0026ndash;Ag NRCs. To elucidate the origin of this enhancement, a comprehensive investigation of the structural, optical, vibrational, and electrochemical properties was carried out using a range of advanced characterization techniques, including high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), diffuse reflectance spectroscopy (DRS), photoluminescence spectroscopy (PL), electrochemical impedance spectroscopy (EIS), Fourier transform infrared spectroscopy (FTIR), UV\u0026ndash;visible spectroscopy, and Raman spectroscopy. HRTEM analysis confirmed the successful formation of heterojunctions within the photocatalyst, revealing the intimate interfacial contact and uniform decoration of Ag nanoparticles on the surface of TiO₂ nanorod like crystals. XRD patterns demonstrated the highly crystalline nature of the synthesized materials, while EIS measurements indicated enhanced separation and transport of photogenerated charge carriers. The improved charge dynamics are attributed to the efficient transfer of electrons from the conduction band of TiO₂ to Ag nanoparticles, which suppresses electron\u0026ndash;hole recombination and prolongs the lifetime of holes within the TiO₂ NRCs. The photocatalytic activity of the TiO₂\u0026ndash;Ag NRCs was systematically evaluated and compared with that of pristine TiO₂ nanoparticles through the degradation of methylene blue dye in an aqueous medium, monitored using UV\u0026ndash;visible spectroscopy. The one-dimensional TiO₂\u0026ndash;Ag nanorod-like crystals exhibited superior photocatalytic efficiency, achieving an exceptional methylene blue degradation efficiency of 99.7%. These results highlight the remarkable potential of TiO₂\u0026ndash;Ag NRCs as highly efficient photocatalysts for the removal of organic pollutants and their promising applicability in addressing serious environmental water contamination challenges.\u003c/p\u003e","manuscriptTitle":"The surface Reactivity of Silver Nanoparticles Doped with TiO 2 Nanorod like crystals for enhancing Photocatalytic Degradation of harmful water pollutants under visible - light irradiations","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2026-03-11 14:33:11","doi":"10.21203/rs.3.rs-8839922/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Revision requested","date":"2026-04-16T09:28:16+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2026-04-14T12:46:39+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"176015026279921002487087835835463153974","date":"2026-04-14T04:43:06+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2026-03-11T04:00:43+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"30477135172235959053081441012437004852","date":"2026-03-06T12:57:48+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"260159089128862303094955628488785403293","date":"2026-03-06T09:03:13+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2026-03-06T08:51:36+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2026-02-14T22:03:53+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2026-02-11T04:11:44+00:00","index":"","fulltext":""},{"type":"submitted","content":"Journal of Nanoparticle Research","date":"2026-02-10T09:44:13+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"journal-of-nanoparticle-research","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"nano","sideBox":"Learn more about [Journal of Nanoparticle Research](http://link.springer.com/journal/11051)","snPcode":"11051","submissionUrl":"https://submission.nature.com/new-submission/11051/3","title":"Journal of Nanoparticle Research","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"caf3ed19-5510-466c-903b-6712924fc576","owner":[],"postedDate":"March 11th, 2026","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"in-revision","subjectAreas":[],"tags":[],"updatedAt":"2026-04-16T09:41:36+00:00","versionOfRecord":[],"versionCreatedAt":"2026-03-11 14:33:11","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-8839922","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-8839922","identity":"rs-8839922","version":["v1"]},"buildId":"XKTyCvWXoU3ODBz1xrDgd","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}