Low silver loaded biphase of TiO2 microrods with TiO2(B)/anatase and their photocatalytic and antibacterial properties

Low silver loaded biphase of TiO2 microrods with TiO2(B)/anatase and their photocatalytic and antibacterial properties | 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 Low silver loaded biphase of TiO 2 microrods with TiO 2 (B)/anatase and their photocatalytic and antibacterial properties Zhijie Ding, Zetan Zhang, Zhitao Chen, Yang Wang, Ruiqi Wang, and 5 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-7513011/v1 This work is licensed under a CC BY 4.0 License Status: Under Review Version 1 posted 9 You are reading this latest preprint version Abstract The TiO 2 microrods (TiO 2 MRs) with TiO 2 (B)/anatase biphase heterojunctions were synthesized through hydrolyzing of precursor K 2 Ti 4 O 9 and calcining of hydrated H 2 Ti 4 O 9 . An optimized amount of silver nanoparticles (AgNPs) loaded on TiO 2 MRs (Ag/TiO 2 MRs) was obtained via solvent evaporation followed by thermal reduction . The photocatalytic degradation rates reached 81.34% for MB over TiO 2 MRs, and 99.81% for RhB over Ag/TiO 2 MRs within 30 minutes under ultraviolet (UV) radiation, which demonstrated that TiO 2 (B)/anatase heterojunctions and Ag-TiO 2 Schottky Barrier markedly enhanced the photocatalytic activity owing to effective separation of photogenerated carriers. Additionally, the scavenger experiments revealed that photoexcited holes (h + ), superoxide (O 2 • − ) and hydroxyl (HO•) radicals were actively involved in the photodegradation of RhB. Furthermore, the slightly improved RhB catalytic degradation rates for Ag/TiO 2 MRs under xenon lamp demonstrated the surface plasmon resonance effect generated from AgNPs. Besides, the well-dispersed AgNPs could act as a controlled-release silver ion reservoir , providing sustained antibacterial activity in the dark. silver nanoparticles TiO2(B)/anatase heterojunctions surface plasmon resonance contact antibacterial photocatalytic mechanism Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 Figure 9 Figure 10 Highlights A heterojunction was obtained by combining AgNPs with phase-tunable TiO 2 (B)/anatase MRs. The Ag-TiO 2 Schottky junction traps electrons, thus enhancing catalytic performance of RhB. Ag/TiO 2 MRs exhibit enhanced visible-light activity due to the surface plasmon resonance effect of AgNPs . Controlled Ag⁺ release from Ag/TiO 2 MRs provides dark antibacterial functionality. 1. Introduction The photocatalyst, titanium dioxide (TiO 2 ), which has the advantages of high photocatalytic efficiency, low cost consumption, and non-toxicity [ 1 – 4 ] , is considered to be one of the most promising semiconductor materials, and has been widely used in the field of photocatalytic degradation of pollutants [ 5 ] , water splitting [ 6 , 7 ] , CO 2 reduction [ 8 – 10 ] , photochromism [ 11 ] and electrochromism [ 12 ] , solar cells [ 13 , 14 ] , and ion batteries [ 15 – 17 ] . TiO 2 exists in multiple polymorphic forms, such as rutile, anatase, brookite, and the bronze phase (TiO 2 (B)). Among these phases, anatase exhibits higher catalytic activity under UV irradiation due to the presence of numerous defects and oxygen vacancies as a electron shallow trap to delay charge recombination in the anatase TiO 2 lattice. TiO 2 (B) is usually synthesized through the transformation of layered titanate precursors [ 18 ] . It has a relatively open structure with free space and continuous channels, which gives it unique advantages in energy storage fields such as lithium-ion batteries [ 19 ] . The common methods for synthesizing TiO 2 include hydrothermal method [ 20 ] , sol-gel method [ 21 ] , high-temperature solid state method [ 22 ] , microemulsion method [ 23 ] , precipitation method [ 24 ] , electrospinning method [ 25 ] . It was well known that solid-state reaction is suitable for large-scale production and industrial production, with the advantages of stable reaction process and simple operation. By the method, layered metastable precursor K 2 Ti 2 O 5 or K 2 Ti 4 O 9 were synthesized [ 26 – 28 ] firstly. The precursor was then hydrolyzed to form hydrated titanic acid (H 2 Ti 4 O 9 ·nH 2 O), which was subsequently calcined to yield TiO 2 . In this study, the layered titanate salt of K 2 Ti 4 O 9 precursor was batch synthesized by Kneading-Drying-Calcination method (KDC) using titanic acid and K 2 CO 3 as raw materials [ 22 ] . Then by controlling the calcination temperature of H 2 Ti 4 O 9 ·nH 2 O, different crystalline phases of TiO 2 were obtained. As the temperature increased to 998.15K, the majority of the metastable phase TiO 2 (B) transformed into anatase, thus yielding a TiO 2 (B)/anatase type Ⅱ heterostructure [ 29 ] , which will effectively promote the separation of electrons and holes. Moreover, noble metal Ag loading is another measure to further reduce carrier recombination. Ag was dispersed on the surface of TiO 2 acting as electron traps, leading to the formation of the Schottky Barrier at the interface as an electronic one-way valve to suppress the rapid recombination of photogenerated electrons and holes. It was observed that loading an appropriate amount of Ag onto TiO 2 not only enhances its photocatalytic activity under UV radiation but also improves its photostability, maintaining higher catalytic degradation performance during repeated cycling tests. Besides, silver could also broaden the spectrum under visible light originated from the surface plasmon resonance effect (SPR) [ 30 , 31 ] . Furthermore, based on the broad spectrum antibacterial performance of silver ions [ 32 ] , the silver-loaded photocatalytic synergistic system can create a highly resistant bacterial environment [ 33 ] , which can be applied in antibacterial coatings, indoor air purification, medical dressings, and surgical fabrics, etc. 2. Experimental section(Materials and methods) 2.1 Materials The starting materials, metatitanic acid (TiO(OH) 2 ), anhydrous potassium caRhBonate (K 2 CO 3 ) were purchased from Aladdin Chemicals Ltd, China. Silver nitrate (AgNO 3 ), absolute alcohol, hydrochloric acid (37%), methylene blue (MB) and Rhodamine B (RhB), were purchased from Sinopharm Chemical Reagent Co, Ltd, China. The quenchers, p-benzoquinone (BQ), tert-Butanol (tBA), and ethylenediaminetetraacetic acid disodium salt dihydrate (Na 2 EDTA) were purchased from Aladdin Chemicals Ltd, China. All the experimental solutions were prepared with Millipore water (18 MΩ.cm) collected from Elix Millipore system. 2.2 K 2 Ti 4 O 9 precursor preparation Pure K 2 Ti 4 O 9 precursors were prepared using the Kneading-Drying-Calcination (KDC) method. The chemical composition, specifically the TiO(OH) 2 /K 2 CO 3 molar ratio, was controlled at 3. The two reactants were mixed in a high-performance ball mill, using absolute ethanol as a grinding aid, and milled for 4 hours at a speed of 350 revolutions per minute (r/min). After drying at 333.15K, the resulting mixture was passed through an 80 mesh sieve. The mixture was then placed into a muffle furnace and sintered at 1273.15K for 1 hour to obtain the K 2 Ti 4 O 9 precursor. The obtained precursor was ground through an 80 mesh sieve for subsequent use and characterization. 2.3 TiO 2 microrods (TiO 2 MRs ) preparation The K 2 Ti 4 O 9 precursor was hydrolyzed in acidic solution to obtain hydrated H 2 Ti 4 O 9 powder after washing and drying. Then the resulting products was putted into a muffle furnace to sinter at 998.15K for 2 h to obtain mesoporous TiO 2 MRs with TiO 2 (B)/anatase heterojunctions. 2.4 Ag/TiO 2 heterostructured microrods (Ag/TiO 2 MRs) preparation 400 mg of TiO 2 MRs were dispersed in 50 mL absolute ethanol, and treated ultrasonically for 30 min to obtain a milky white colored suspension. 8.5 mg silver nitrate (the atom ratio of silver to titanium is 1 to 100) was dispersed in 10 mL absolute ethanol, and added 5 μL ammonia to get a transparent solution. Then the prepared silver nitrate alcohol solution was mixed with the TiO 2 suspension by sonication and the mixture was heated to remove the absolute ethanol and collect powder. Finally, put the collected powder into a muffle furnace to calcine at 573.15K for 1 h. The obtained sample was denoted as Ag/TiO 2 MRs-A. The Ag/TiO 2 MRs with different silver contents were prepared using 25.5 mg (the atom ratio of silver to titanium is 3 to 100) and 42.5 mg (the atom ratio of silver to titanium is 5 to 100) of AgNO 3 (instead of 8.5 mg) and the corresponding samples were denoted as Ag/TiO 2 MRs-B and C, respectively. 2.5 Structural characterization X-ray powder diffraction (XRD) patterns of TiO 2 MRs and the Ag/TiO 2 HNRs samples were obtained using a Shimadzu 6100 X-ray diffractometer (Japan) with a Cu Kα radiation with a wavelength (λ) of 0.15418 nm and at a scan rate (2θ) of 10° min –1 . The morphologies of the samples were examined by field emission scanning electron microscopy (FE-SEM, TESCAN, MIRA3) , and a high-resolution transmission electron microscope (HRTEM, JEM-2100F, JEOL, Japan). UV-Visible absorption spectroscopy (ABs) and UV-Vis diffuse reflectance spectra (DRS) were carried out by using a Shimadzu UV-1800 spectrophotometer and Shimadzu UV-3600 spectrophotometer, respectively. The pore structure and surface area of the samples were performed by nitrogen adsorption and desorption method using advanced specific surface area and micropore analyzer (BSD-660M, China). 2.6 Optical Performance and photoelectrochemical performance Analysis The separation ability of photo generated electron hole pairs was evaluated by photoluminescence spectroscopy (PL, Shimadzu, RF-6000 fluorescence spectrometer) with an excitation wavelength of 360 nm. To obtain the optoelectronic properties of catalysts, the transient photocurrent was examined by electrochemical workstation (CHI660E, China) and electrochemicalimpedance spectroscopy (EIS) was examined by electrochemical workstation (Zahner-PP211, Germany). The transient photocurrent was performed in a conventional three-electrode cell using the indium tin oxide (ITO) substrate deposited the catalyst powder, a Pt plate and an Ag/AgCl electrode as working photoelectrode, the counter electrode and reference electrode, respectively. The photocurrent response of the samples was performed in a 0.5M Na 2 SO 4 aqueous solution under 0.5 volts voltage. 2. 7 Photocatalytic tests The photocatalytic activities of TiO 2 MRs and Ag/TiO 2 MRs with different silver contents were evaluated by degrading MB or RhB solution. Twenty milligrams of the photocatalyst and 100 mL of 10mg/L of the MB or RhB solution were added into a water-cooled photochemical reactor, and were stirred for 30 min to reach the desorption−absorption equilibrium in a dark box. Four milliliter aliquots were collected and then filtered with a micropore filter (0.45 μm) to remove the as-prepared photocatalysts, the filtrate was determined using UV–Vis spectrophotometer and the concentration of solution was labeled as C 0 . A 500 W high-pressure mercury lamp was used to irradiate the suspension. The irradiance at the reaction liquid level, measured with an optical power density radiometer (CEL-NP2000-2A, China), was 7.98 mW/cm² at the main wavelength of 365 nm. At given time intervals, the concentration of solution was examined which was labeled as C t . The following equation estimated the degradation efficiency. The degradation of RhB was conducted under a 500 W xenon lamp to verify the role of silver nanoparticles in expanding the visible light response range due to the SPR effect. Thirty milligrams of the photocatalyst were added to 100 mL of a 10 mg/L RhB solution in a water-cooled photochemical reactor. The irradiance at the reaction liquid level, measured across the 290-800 nm wavelength range, was 18.60 mW/cm². 2. 7 Antibacterial tests in the dark Sterile filter paper disks with a diameter of 1cm were immersed in 2mg/mL suspension of antibacterial samples for 10 minutes. 0.1mL of bacterial solution with a Staphylococcus aureus ( S. aureus ) content of 10 4 CFU/mL was evenly coated onto the surface of Mueller Hinton agar plate culture medium. The above soaked filter paper disks were attached to the surface of the culture medium. Then the culture medium s with filter papers were placed in a 310.15K constant temperature incubator with a humidity of 80% for 20 hours. Finally‌, the diameters of the inhibition zone were measured with a vernier caliper, accurated to 0.1 mm. The antibacterial experiment was repeated three times for each sample and the average value was obtained. 3. Results and discussion 3.1 Characterization analysis 3.1.1 XRD analysis The crystal structures and phase of TiO 2 MRs and Ag/TiO 2 MRs with different silver content were characterized by XRD, as shown in Figure 1. It can be observed that all the samples show a mixed phase of anatase and TiO 2 (B), and anatase is the main phase from the diffraction peaks .The peaks at around 2θ = 25.28°, 36.95°, 37.80°, 38.58°, 48.05°, 53.89° and 55.06° are attributed to anatase TiO 2 (JCPDS NO.21-1272), corresponding to (101), (103), (004), (112), (200), (105) and (211) crystal planes, respectively. The weak peaks at around 2θ = 24.93°, 28.61° , 29.70°, 33.32°, 43.51°, 44.50° and 48.53° are attributed to metastable TiO 2 (B) (JCPDS NO.46-1237), corresponding to (110), (002), (40 1 ( — ) ), (31 1 ( — ) ), (003), (60 1 ( — ) ) and (020) crystal planes, respectively. It can be seen that the peak intensities of (110) and (020) crystal planes of metastable TiO 2 (B) decreased obviously with the increasing silver loading in Ag/TiO 2 MRs samples, meaning further transformation from metastable TiO 2 (B) phase to anatase phase. It was revealed that the heterophase junction formed between TiO 2 (B) and anatase, which was the responsible for the high charge-separation efficiency in mixed phase photocatalysts. Moreover, the crystal phase peak at 38.12° corresponding to the (111) crystal pane, which was attributed to metallic Ag (JCPDS NO.04-0783), was discovered in the patterns of Ag/TiO 2 MRs-B and C. Due to low silver loading, there was no occurrence of diffraction peak for elemental silver in Ag/TiO 2 MRs-A. 3.1.2. FE- SEM and HRTEM-EDX analysis SFig.1 shows FE-SEM images of TiO 2 MRs and Ag/TiO 2 MRs-B at lower magnification and higher magnification. The TiO 2 MRs sample (SFig.1a and 1c) exhibits an microrod morphology with a length shorter than 5 μm. The Ag/TiO 2 MRs-B (SFig.1b and 1d) has a similar morphology to that of pure TiO 2 MRs. To further observe the morphology and structure of TiO 2 MRs and Ag/TiO 2 MRs, TEM image of Ag/TiO 2 MRs-B was recorded, as illustrated in Fig.2. As can be seen in Fig.2a, AgNPs were bound on the surface of TiO 2 MRs, indicating the formation of composite nanostructures. In Fig.2b, the HRTEM image revealed obvious lattice planes with spacings of ~0.351 and ~0.326 nm, which were correspond to the (101) plane of anatase TiO 2 and the (111) plane of metallic Ag [ 34 , 35 ] , respectively. In addition, the elemental mapping results (Fig.2c–e) also demonstrated the presence of low Ag on the TiO 2 surface. According to the above results, metallic Ag was successfully loaded on the TiO 2 surface to form Ag/TiO 2 heterojunction by the present facile strategy. The lattice stripes of the (110) plane of TiO 2 (B) could not be identified due to the small proportion of TiO 2 (B) phase or the similarity of the lattice stripes of the (101) plane of anatase TiO 2 and the (110) plane of TiO 2 (B). 3.1.3. XPS analysis The successful loading of Ag on the TiO 2 surface was further investigated by XPS, which revealed the surface composition and their chemical states in the Ag/TiO 2 MRs. The XPS spectrum in Fig.3a displayed that the Ag/TiO 2 MRs-B sample was composed by Ti, O, C, and Ag. The Ag/TiO 2 MRs (Fig.3b) displayed two peaks with the binding energies of 368.4 eV, and 374.4 eV, indicating the presence of metallic silver (Ag 0 ) [ 36 ] , which were ascribed to Ag 3d 5/2, and Ag 3d 3/2 of Ag/TiO 2 MRs-B, respectively. As displayed in Fig.3c, the binding energies of 458.4 eV and 464.1 eV are attributed to Ti 2p 3/2 and Ti 2p 1/2 in Ag/TiO 2 MRs-B, respectively, confirming the presence of Ti (VI). As shown in Fig.3d, the peak at 529.8 and 531.4 eV can be attributed to the O 1s XPS profiles of all the samples. 3.1.4 UV - Vis DRS analysis To further identify the successful loading of Ag, the ultraviolet-visible diffuse reflectance spectra (DRS) of all the samples were shown in SFig.2. It can be seen that the absorption edges of Ag/TiO 2 MRs showed red-shift slightly compared to bare TiO 2 MRs with the increase of Ag content as displayed in SFig.2a.The relationship between (F hv ) 1/2 and photon energy of samples was calculated by the Kubelka-Munk formula (F hν ) 1/n =K/S=(1-R) 2 /2R= B( hν - E g ), Where the K, S, R, h , ν , and E g represent absorption coefficient, the reflection coefficient, reflectivity (%), Planck's constant, the frequency of the light, and the bandgap energy, n=1/2 for direct bandgap semiconductor, n=2 for indirect bandgap semiconductor. The results shown in SFig.2b indicate that the bandgap energy of TiO 2 MRs, Ag/TiO 2 MRs-A, Ag/TiO 2 MRs-B and Ag/TiO 2 MRs-C samples are 3.19 eV, 3.16 eV, 3.13 eV and 3.08 eV, respectively, suggesting that the loading of silver on the surface slightly reduced the bandgap width. 3.1.5 N 2 adsorption - desorption analysis As shown in SFig.3 the N 2 adsorption‐desorption isotherms of TiO 2 MRs and Ag/TiO 2 MRs-B displayed type IV according to the BDDT (Deming and Teller) classification. When p/p 0 is in the range of 0.8 to 1, and hysteresis loops are similar to H3 type, indicating the presence of mesopores, which may be related to layered structure of K 2 Ti 4 O 9 precursors [ 19,37 ] . The pore size distribution curve (inset in SFig.3) revealed that the prepared TiO 2 MRs and Ag/TiO 2 MRs-B mainly contained mesopores and macropores. The specific surface area, the pore volume and the average pore diameter of TiO 2 MRs are 16.2 m 2 /g, 0.066 cm 3 g –1 and 16.42 nm, respectively. Ag/TiO 2 MRs-B demonstrated the slightly lower specific surface area, the slightly higher pore volume, and the slightly higher average pore diameter: 13.8 m 2 /g, 0.069 cm 3 ·g –1 , and 19.48 nm, respectively. This result of low specific surface area is consistent well with the result of SEM displayed microrods morphology rather than nanoscale. Furthermore, in the TiO 2 microrods preparation process at 998.15K, only a small number of slit pores can be preserved, resulting in a small pore volume. After loading silver, the specific surface area slightly decreased, suggesting that a small amount of larger silver particles embedded in the slit increased the pore volume and pore size. 3. 2 Photoelectrochemical characterization The dynamic characteristics of photogenerated charge carriers in catalysts were explored through PL, photocurrent and EIS Analysis. It can be seen from SFig.4 that compared with TiO 2 MRs, the PL emission peak intensity of Ag/TiO 2 MRs-B is significantly lower than that of TiO 2 MRs, indicating that the loading of AgNPs reduces the recombination rate of photo generated electron-hole pairs. Under the same experimental conditions, the lifetime of charge carriers in Ag/TiO 2 MRs-B was extended and the catalytic performance was improved. In order to furtherly investigate the effect of AgNPs on the photoelectric properties of TiO 2 microrods, the photocurrent of TiO 2 MRs and Ag/TiO 2 MRs-B were tested under 365 nm ultraviolet light irradiation. Fig. 4a shows that Ag/TiO 2 MRs-B exhibited a photocurrent density of 270 ± 5 nA, which is 56% higher than that of TiO 2 MRs (173 ± 5 nA). This improvement of charge separation could be attributed to electron trap effect of Ag and the formation of the Schottky junction, which is consistent with the PL measurements. As shown in Fig. 4b, EIS measurements for TiO 2 MRs and Ag/TiO 2 MRs-B were performed under 365 nm illumination . An equivalent circuit diagram with two semicircles was displayed through Z-View fitting (SFig.5). Evidently, the impedance diagram showed that the radius of the arc of Ag/TiO 2 MRs-B (the charge-transfer resistance 9617 ohm) is smaller than TiO 2 MRs (32539 ohm), indicating that TiO 2 MRs loaded AgNPs composite are more conducive due to improving the transfer efficiency of charges at the electrode electrolyte interface and enhancing optoelectronic performance. 3. 3 Photocatalytic activity on M B solution under ultraviolet radiation The photodegradation efficiency of MB for TiO 2 MRs and Ag/TiO 2 MRs with different silver content was displayed in Fig.5a. Ag/TiO 2 MRs-B showed the highest photocatalytic activity and the MB degradation efficiency was 93.11% within 30 min, which demonstrated an optimized amount of AgNPs on TiO 2 could promote the photocatalytic activity. Comparatively, the MB degradation efficiency was 81.34% for TiO 2 MRs. In spite of lower than that of Ag/TiO 2 MRs-B, it was still a higher degradation efficiency, which was attributed to the efficient charge separation of TiO 2 (B)/anatase heterostructures. However, the degradation efficiency of 89.40%and 80.17% for Ag/TiO 2 MRs-A and Ag/TiO 2 MRs-C showed the insufficient or excessive loading of AgNPs were unfavorable to the photocatalytic process. It is speculated that the insufficient silver loading was unable to form an effective Schottky junction. However, the excessive silver loading led to the aggregation of silver particles, which not only shields the active sites but may also become recombination centers, thereby decreasing the activities. The degradation of MB obeyed pseudo-first order kinetics (shown in Fig.5b), which was indicated using ln(c 0 /c t ) = k t, where c 0 and c t are the initial and remaining MB, respectively; k is the kinetics rate constant; and t is the UV light radiation time. Ag/TiO 2 MRs-B had the largest reaction rate and enhanced MB degradation by 1.60 times higher efficiency than TiO 2 MRs (shown in STable 1). The catalytic efficiency of both TiO 2 MRs and Ag/TiO 2 MRs-B composite increased as the usage of catalysts increased from 20 mg to 30 mg, especially, the MB degradation efficiency for Ag/TiO 2 MRs-B composite increased from 84.52% to 99.80% in 20 min (shown in Fig.5c). Fig.5d displayed the result of the stability test for Ag/TiO 2 MRs-B through four cycles of use (20mg, 30min). The MB degradation efficiency decreased lightly and yet remained 91.00% for the fourth cycle, which confirms that Ag/TiO 2 MRs-B have a good photostability. 3. 4 Photocatalytic activity on RhB solution under ultraviolet radiation and the calculation of activation energy E a The degradation efficiency of RhB was shown in Fig.6a. The degradation efficiency of RhB using TiO 2 MRs reached only 50.94% within 30 minutes, which was significantly lower than the 81.34% efficiency observed for MB under identical conditions. It was inferred that there was a lack of strong electrostatic adsorption between the negatively charged TiO 2 surface and the electrically neutral RhB molecules at neutral pH. And the highly stable conjugated xanthene chromophore structure of RhB was another reason for the low degradation rate. Nevertheless, loading with AgNPs significantly enhanced the RhB degradation efficiency of the TiO 2 MRs, which has already been proved that the RhB degradation efficiency reached 93.17%, 96.71%, and 89.74% for Ag/TiO 2 MRs-A, B, and C, respectively. The degradation rate of RhB obeyed pseudo-first order kinetics as well (shown in Fig.6b). It was found that the apparent rate constant of RhB with Ag/TiO 2 MRs-A, Ag/TiO 2 MRs-B and Ag/TiO 2 MRs-C was approximately 0.08949 min -1 , 0.11382 min -1 , and 0.07529 min -1 , which were 3.77, 4.80 and 3.18 times higher than that of TiO 2 MRs , respectively (shown in STable 2). Ag/TiO 2 MRs-B enhanced MB and RhB degradation by 1.60 times and 4.80 times higher efficiency than TiO 2 MRs, which demonstrated that there were differences in the degradation pathways of MB and RhB and the AgNPs introduced new catalytic sites that prominently altered and accelerated the degradation pathway of RhB. The degradation efficiency and reaction rate at 285.15K, 296.15K and 308.15K were examined (as shown in Fig.6c and 6d), and it was shown that photocatalytic degradation rate constants have been increased with the rising of temperature. The RhB degradation efficiency was 46.63%, 66.07%, 80.85% in 10min, respectively. Based on the photocatalytic reaction rates at different temperatures combined with Arrhenius equation, the apparent activation energy (E a ) of catalyst was estimated as 22.73 KJ/mol. (STable 3). 3. 5 Mechanism of photodegradation dye under ultraviolet radiation To understand the photocatalytic mechanism of degradation organic dyes, the scavenging experiments were carried out to investigate the radicals during the reaction. The quenchers, including ethylenediaminetetraacetic acid disodium salt (Na 2 EDTA), p-benzoquinone (BQ) and tert-Butanol (tBA) were employed as h + , •O 2 - and HO• scavengers, respectively. As Fig.7 shown, with increasing scavenger addition dose, it was observed that a higher quenching effect on the dye degradation over Ag/TiO 2 MRs-B (30mg) was achieved, moreover, the addition of scavengers had a greater impact on RhB solution than on MB solution. For MB solution (Fig.7a and 7b) as the addition doses of Na 2 EDTA were 0.5 mmol/L and 1 mmol/L, the addition doses of BQ were 0.5 mmol/L and 1 mmol/L, the addition doses of tBA were 10 mmol/L and 50 mmol/L, the degradation efficiency in 20 min decreased from 99.80% to 81.23% and 69.19%, to 82.20% and 67.86%, to 92.29% and 83.52%, respectively. Comparatively, for RhB solution (Fig.7c and 7d) at the same condition, the degradation efficiency decreased from 99.81% to 64.60% and 24.31% , to 49.55% and 34.41%, to 59.90% and 48.53%, respectively. The results suggested that active species h + , •O 2 - , and HO• played a crucial role in the reaction mechanism for RhB degradation. The reason is that the highly stable conjugated xanthene chromophore structure of RhB is more easily attacked and destroyed by h + and HO•. The hinderance effect of electronic flow on Schottky junction between Ag-TiO 2 interface effectively separates photogenerated charges, thus significantly increase the number of h + available for oxidation of RhB. While the degradation pathway of MB, in addition to the traditional semiconductor photocatalytic mechanism, also includes the predominant dye self-sensitization mechanism, where the source of electrons is the dye molecules themselves and is significantly different from the process of electrons generated by photoexcitation of TiO 2 . The possible photocatalytic mechanism of Ag/TiO 2 HMRs for MB and RhB degradation was proposed and shown in Fig.8. The photocatalytic efficiency of a semiconductor is primarily governed by its energy band structure, including the band gap value and the positions of the valence band edge (VBE) and conduction band edge (CBE). The band gap energies of anatase and TiO 2 (B) are 3.20~3.23eV and 3.09~3.22eV [ 38 ] , sharing a similar band gap, but they exhibit distinct band edge alignments that the conduction band bottom and valence band top of anatase lie at a lower energy level than those of TiO 2 (B) [ 39,40 ] .When a TiO 2 (B)/anatase mixed-phase system is formed, a heterophase junction (a typical Type-II heterojunction) is formed at the interface. Meanwhile, an internal electric field occurs inducing from the difference in band edge positions, which drives photogenerated electrons toward one phase and holes toward the other, thus resulting in highly efficient charge separation. Under UV irradiation, when photogenerated electrons transfer from the conduction band of TiO 2 (B) to the slightly lower conduction band of anatase, accumulating within the anatase phase, photogenerated holes migrate from the valence band of anatase to that of TiO 2 (B), accumulating on the TiO 2 (B) side. Furthermore, low Ag loading dramatically improved the carriers separation efficiency via electron transfer process from the conduction band of TiO 2 to the adjacent AgNPs, which possess a higher work function. Thus, in Ag/TiO 2 MRs, a Schottky barrier at the metal-semiconductor interface was formed, which acted as an efficient electron trap, suppressing carrier recombination and enabling electron transfer to molecular oxygen (O 2 ) to form superoxide anion radicals (·O 2 ⁻). As a consequence, this composite significantly facilitates interfacial charge transfer and reduces the recombination of electron-hole pairs. 3. 6 Expanding spectra and antibacterial effect of AgNPs Similarly, AgNPs in the composite not only act as traps to capture electrons, but also play an extended spectral role under a xenon lamp simulating sunlight. The RhB degradation reaction obeyed pseudo-first order kinetics as well. When RhB solution was irradiated for 150 minutes, the RhB degradation efficiency was 88.29%, 89.57%, 94.80% and 93.5% for TiO 2 MRs, Ag/TiO 2 MRs-A, Ag/TiO 2 MRs-B and Ag/TiO 2 MRs-C, respectively(as shown in Fig.9 ). The slight enhancement of catalytic activity of silver loaded samples indicated that elemental silver extended the response range from ultraviolet to visible light through SPR effect. Invariably, the Ag/TiO 2 MRs-B exhibited the strongest performance in RhB degradation under simulated sunlight , the apparent rate constant were 1.36 times higher than that TiO 2 MRs than that of TiO 2 MRs ( STable 4 ). The antibacterial activity of TiO 2 MRs and Ag/TiO 2 MRs with different silver content against S. aureus in the dark was evaluated by using the disk diffusion method, as shown in Fig.10. Ag/TiO 2 MRs-B and Ag/TiO 2 MRs-C showed weak inhibition with a zone diameter of 12.5 mm and 12.2 mm, while TiO 2 MRs and Ag/TiO 2 MRs-A exhibited no inhibition ， as shown in Fig.10 and STable 5. AgNPs inhibit bacterial growth in the dark through direct contact mechanisms, including disruption of cell membrane integrity and interference with DNA replication. When AgNPs coexist with titanium dioxide, the composite exhibits a synergistic effect, which could be verified by subsequent experiments. 4. Conclusions In this work, a biphase composite TiO 2 MRs and optimized silver loading Ag/TiO 2 MRs exhibited significantly enhanced activity under both UV and simulated solar light irradiation. Photoelectrochemical and PL characterization further confirmed the effect of AgNPs on the migration, transportation, and recombination processes of photogenerated charge carriers. The degradation pathways of RhB and MB over Ag/TiO 2 MRs were inferred by the scavenging experiments. The inhibition zone experiment in the dark confirmed that Ag/TiO 2 MRs functions as a silver ion reservoir. This article offered a valuable strategy for catalyst design in the batch synthesis of TiO 2 MRs and their application in dye degradation. The findings of this work was expected to provide an efficient and sustainable solution to address environmental pollution and public health issues. Declarations Funding This work was supported by Anhui Province Applied Peak Cultivation Discipline (No. XK-XJGF005) and Anhui Province Key Research and Development Program ( No. 202304a05020085). Conflict of interest No conflict of interest exits in the submission of this manuscript, and all the authors listed have approved the manuscript that is enclosed. Author contributions ZD, ZZ, ZC, YW, RW and XX performed the experiment, ZD wrote the original draft. LB, YL, XW, and YG supervised, reviewed, and edited, and provided the resources. References Khan SUM, Al-Shahry M, Ingler WB (2003) Efficient Photochemical Water Splitting by a Chemically Modified n-TiO 2 . Science 297(5590):2243-2245. https://doi.org/10.1126/science.1075035 Basavarajappa PS, Patil SB, Ganganagappa N, Reddy KR, Raghu AV, Reddy CV (2020) Recent progress in metal-doped TiO 2 , non-metal doped/codoped TiO 2 and TiO 2 nanostructured hybrids for enhanced photocatalysis. Int J Hydrogen Energ 45(13):7764-7778. https://doi.org/10.1016/j.ijhydene.2019.07.241 Rasouli K, Alamdari A, Sabbaghi S (2023) Ultrasonic-assisted synthesis of α-Fe 2 O 3 @TiO 2 photocatalyst: Optimization of effective factors in the fabrication of photocatalyst and removal of non-biodegradable cefixime via response surface methodology-central composite design. Sep Purif Technol 307:122799. https://doi.org/10.1016/j.seppur.2022.122799 Hamza ZA, Dawood JJ, Jabbar MA (2024) Review of TiO 2 as Desulfurization Catalyst for Petroleum. Catalysts 14(6):381-400. https://doi.org/10.3390/catal14060381 Sathishkumar K, Sowmiya K, Arul Pragasan L, Rajagopal R, Sathya R, Ragupathy S, Krishnakumar M, Reddy VRM (2022) Enhanced photocatalytic degradation of organic pollutants by Ag-TiO 2 loaded cassava stem activated caRhBon under sunlight irradiation.Chemosphere 302:134844. https://doi.org/10.1016/j.chemosphere.2022.134844 Backus EHG, Hosseinpour S, Ramanan C, Sun S, Schlegel SJ, Zelenka M, Jia XY, Gebhard M, Devi A, Wang HI, Bonn M (2024) Ultrafast Surface-specific spectroscopy of water at a photoexcited TiO 2 model water-splitting photocatalyst. Angew Chem Int Ed 63 (8):e202312123. https://doi.org/10.1002/anie.202312123 Nguyen CQQ, Zhu GP, Jia DM, Ye W, Wang YK, Wang J, Ting T, Xu FC, Gan J, Li WH, Gao P (2021) Built-in electric field for photocatalytic overall water splitting through a TiO 2 /BiOBr P-N heterojunction. Nanoscale 13 (8):4496-4504. https://doi.org/10.1039/d0nr08928a Ahmadi M, Alavi SM, Larimi A (2023) Pt–Cu@Bi 2 MoO 6 /TiO 2 Photocatalyst for CO 2 Reduction.Inorg.Chem 62 (49):20372-20389. https://doi.org/10.1021/acs.inorgchem.3c03372 Nguyen TP, Dang LTN , Nguyen VH, Le TH, Vo DVN，Trinh QT, Bae SR, Sang YC, Kim SY, Le QV (2020) Recent Advances in TiO 2 -Based Photocatalysts for Reduction of CO 2 to Fuels. Nanomaterials 10(2):337. https://doi.org/10.3390/NANO1002033 Firoozabadi SR, Khosravi-Nikou MR, Shariati A (2023) CO 2 photoreduction using TiO 2 nanoflower /UiO-66 composite under UV light irradiation. J Environ Chem Eng 11 (5):110978. https://doi.org/10.1016/j.jece.2023.110978 Belhomme L, Duttine M, Labrugère C, Coicaud E, Rougier A, Penin N, Dandre A,Ravaine S,Gaudon M (2024) Investigation of the Photochromism of WO 3 ,TiO 2 , and Composite WO 3 -TiO 2 Nanoparticles. Inorg Chem 63(21):10079-10091. https://doi.org/10.1021/acs.inorgchem.4c01379 Soltani S, Ardyanian M, Shahidi MM (2024) Enhancement of electrochromic efficiency of TiO 2 nanorods. Opt mater 152:115484. https://doi.org/10.1016/j.optmat.2024.115484 Nivethitha R, Neha P, Aarthi K, Jeyadheepan K, Gandhi S (2025) Enhancing the efficiency of dye sensitized solar cells using TiO 2 / Sr 1-x CaSiO 4 : x Tb 3+ nanocomposite as a photoelectrode modifier. Journal of power sources 641:236877. https://doi.org/10.1016/j.jpowsour.2025.236877 14. Wen Z, Liang C, Li S, Wang G, He B, Gu H, Xie J, Pan H, Su Z, Gao X, Hong G, Chen S (2024) High-Quality van der Waals Epitaxial CsPbBr 3 Film Grown on Monolayer Graphene Covered TiO 2 for High-Performance Solar Cells. Energy & Environmental Materials 7(4):12680. https://doi.org/10.1002/eem2.12680 15. Wang X, Cheng W, Hu J, Yu H, Kong X, Uemura S, Kusunose T, Feng Q (2022) Topochemical synthesis of Mn 2 O 3 /TiO 2 and MnTiO 3 /TiO 2 nanocomposites as lithium-ion battery anodes with fast Li + migration and giant pseudocapacitance via the mesocrystalline effect, Nanoscale 14(37):13696-13710. https://doi.org/ 10.1039/d2nr03516b Ren Y, Liu Z, Pourpoint F, Armstrong AR, Grey CP, Bruce PG (2012) Nanoparticulate TiO 2 (B): an anode for lithium-ion batteries. Angew Chem Int Ed 51(9):2164-2167. https://doi.org/10.1002/anie.201108300 Wang SH, Zhu YY, Sun XJ, An SL, Cui JL, Zhang YQ, He WX (2021) Microwave synthesis of N-doped modified graphene/mixed crystal phases TiO 2 composites for Na-ion batteries. Colloid Surface A 615:126276. https://doi.org/10.1016/j.colsurfa.2021.126276 Feist TP, Davies PK (1992) The soft chemical synthesis of TiO 2 (B) from layered titanates. J Solid State Chem ‌‌101(2):275-295. https://doi.org/10.1016/0022-4596(92)90184-w Wei H, Rodriguez EF, Hollenkamp AF, Bhatt AI, Chen DH, Caruso RA (2017) High reversible pseudocapacity in mesoporous Yolk-shell anatase TiO 2 /TiO 2 (B) microspheres used as anodes for Li-ion batteries. Adv Funct Mater 27(46):1703270. https://doi.org/10.1002/adfm.201703270 Zhang E, Pan Y, Lu T, Zhu Y, Dai W (2020) Novel synthesis of S‑doped anatase TiO 2 via hydrothermal reaction of Cu–Ti amorphous alloy. Applied Physics A 126:606. https://doi.org/10.1007/s00339-020-03790-1 Ansari F, SheibaniS, Caudillo-Flores U. et al. Effect of TiO 2 nanoparticle loading by sol–gel method on the gas-phase photocatalytic activity of CuxO–TiO2 nanocomposite. J Sol-Gel Sci Technol 96, 464–479 (2020). https://doi.org/10.1007/s10971-020-05388-8 Wang XY, Xie KY, Li J, Lai YQ, Zhang ZA, Liu YX (2011) Synthesis and electrochemical performance of TiO 2 -B as anode material. J Cent South Univ 18(2):406-410. https://doi.org/10.1007/s11771-011-0711-9 Zielińska A, Kowalska E, Sobczak JW, Łącka I, Gazda M, Ohtani B, Hupka J, Zaleska A (2010) Silver-doped TiO 2 prepared by microemulsion method: Surface properties, bio- and photoactivity. Sep Purif Technol 72(3):309-318. https://doi.org/10.1016/j.seppur.2010.03.002 Yin S, Ihara K, Aita Y, Komatsu M, Sato T (2006) Visible-Light Induced Photocatalytic Activity of TiO 2- xAy (A=N,S) Prepared by Precipitation Route. J Photoch Photobio A 179(1-2):105-114. https://doi.org/10.1016/j.jphotochem.2005.08.001 Welna DT, Bender JD, Wei XL, Sneddon LG, Allcock HR (2005) Preparation of Boron-CaRhBide/CaRhBon Nanofibers from a Poly(noRhBornenyldecaborane) Single-Source Precursor via Electrostatic Spinning. Adv Mater 17(7):859-862. https://doi.org/10.1002/adma.200401257 He M, Lu XH, Feng X, Yu L, Yang ZH (2004) A simple approach to mesoporous fibrous titania from potassium dititanate. Chem Commun 10(19):2202-2203. https://doi.org/10.1039/b408609k Bao NZ, Feng X, Lu XH, Shen LM, Yanagisawa K (2004) Low-temperature controllable calcination syntheses of potassium dititanate. Aiche J 50(7):1568-1577. https://doi.org/10.1002/aic.10167 Zhu YH, Li W, Zhou YX, Lu XH, Feng X, Yang ZH (2009) Low-Temperature CO Oxidation of Gold Catalysts Loaded on Mesoporous TiO 2 Whisker Derived from Potassium Dititanate. Catal Lett 127(3):406-410. https://doi.org/10.1007/s10562-008-9710-3 Sarkar D, Chattopadhyay KK(2014)Branch density-controlled synthesis of hierarchical TiO 2 nanobelt and tunable three-step electron transfer for enhanced photocatalytic property. Acs Appl Mater Interfaces 6(13):10044-10059. https://doi.org/10.1021/am502379q Zhang ZY, Hu YZ, Fu Z, Li ZH, Chen JD, Yuan M, Wu SX, Hong RD, Lin DQ, Chen XP, Cai JF, Wu ZY, Zhang YN, Fu DY, Shen ZW, Wang ZJ, Zhang F, Zhang R (2025) Localized Surface Plasmon Resonance-Enhanced SiC UV Photodetectors Based on Ordered Al/Al 2 O 3 Core-Shell Nanoparticle Arrays. Small (Weinheim an der Bergstrasse, Germany) 2025:2502011. https://doi.org/10.1002/smll.202502011 Li J, Xie GZ, Jiang J, Liu YY, Chen CX, Li WX, Huang JL, Luo XL, Xu M, Zhang QP, Yang M, Su YJ.(2023) Enhancing photodegradation of Methyl Orange by coupling piezo-phototronic effect and localized surface plasmon resonance. Nano energy 108:108234. https://doi.org/10.1016/j.nanoen.2023.108234 Maniah K, Al-Otibi OF, Mohamed S, Said BA, AbdelGawwad RM, Yassin TM (2024) Synergistic antibacterial activity of biogenic AgNPs with antibiotics against multidrug resistant bacterial strains[J]. Journal of King Saud University. Science 36 (10):103461. https://doi.org/10.1016/j.jksus.2024.103461 Zhang FZ, Zeng Y, Zheng MY, Zheng H, Fang M, Xie BX, Lin RG (2024) Photocatalytic activity and synergistic antibacterial effects of PCN-222@AgNPs under visible light irradiation. Journal of coordination chemistry 77(1-2):188-202. https://doi.org/10.1080/00958972.2024.2303734 Wang P, Lu YG, Wang XF, Yu HG(2017) Co-modification of amorphous-Ti (IV) hole cocatalyst and Ni(OH) 2 electron cocatalyst for enhanced photocatalytic H 2 -production performance of TiO 2 . Appl Surf Sci 391:259-266. https://doi.org/10.1016/j.apsusc.2016.06.108 Kong LG, Dong YM, Jiang PP, Wang GL, Zhang HZ, Zhao N (2016) Light-assisted rapid preparation of a Ni/g-C 3 N 4 magnetic composite for robust photocatalytic H 2 evolution from water. J Mater Chem A 4(25):9998-10007. https://doi.org/10.1039/c6ta03178a Bai L, Zhang XL, Ding ZJ, Wang XC, Huang YJ, Kannan P (2019) One-pot synthesis of Ag nanoparticles/ZnO nanorods heterostructures for organic dyes decoloring. J Taiwan Inst Chem E 103:118-125. https://doi.org/10.1016/j.jtice.2019.08.002 Zhang WF, Zhang Y, Yu L, Wu NL, Huang HT, Wei MD (2019) TiO 2 -B nanowires via topological conversion with enhanced lithium-ion intercalation properties. J Mater Chem A 7 (8):3842-3847. https://doi.org/10.1039/c8ta10709b Opra DP, Gnedenkov SV,Sinebryukhov SL(2019)Recent efforts in design of TiO 2 (B) anodes for high-rate lithium-ion batteries: A review. J. Power Sources 442: 227225. https://doi.org/10.1016/j.jpowsour.2019.227225 Bai Y, Li E, Liu C, Yang ZH, Feng X, Lu XH, Chan KY (2009) Stability of Pt Nanoparticles and Enhanced Photocatalytic Performance in Mesoporous Pt (Anatase/TiO 2 (B)) Nanoarchitecture. J Mater Chem 19(38):7055-7061. https://doi.org/10.1039/b910240j Eddy DR, Permana MD, Sakti LK, Sheha GAN, Solihudin, Hidayat S, Takei A, Kumada N, Rahayu I (2023) Heterophase Polymorph of TiO 2 (Anatase, Rutile, Brookite, TiO 2 (B)) for Efficient Photocatalyst: Fabrication and Activity. Nanomaterials 13(4):704. https://doi.org/10.3390/nano13040704 Additional Declarations No competing interests reported. Supplementary Files Supportinginformation.docx FulluncroppedGelsandBlotsimages.doc GraphicalAbstract.png Cite Share Download PDF Status: Under Review Version 1 posted Editorial decision: Revision requested 27 Sep, 2025 Reviews received at journal 26 Sep, 2025 Reviews received at journal 14 Sep, 2025 Reviewers agreed at journal 06 Sep, 2025 Reviewers agreed at journal 04 Sep, 2025 Reviewers invited by journal 04 Sep, 2025 Editor assigned by journal 03 Sep, 2025 Submission checks completed at journal 03 Sep, 2025 First submitted to journal 01 Sep, 2025 You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. 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-7513011","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":511107566,"identity":"73cadb8d-0b42-4f42-9766-358517ca00d5","order_by":0,"name":"Zhijie Ding","email":"","orcid":"","institution":"Anhui Science and Technology University","correspondingAuthor":false,"prefix":"","firstName":"Zhijie","middleName":"","lastName":"Ding","suffix":""},{"id":511107567,"identity":"b769e793-1bed-495c-98cf-b57d8e09148d","order_by":1,"name":"Zetan Zhang","email":"","orcid":"","institution":"Anhui Science and Technology University","correspondingAuthor":false,"prefix":"","firstName":"Zetan","middleName":"","lastName":"Zhang","suffix":""},{"id":511107568,"identity":"2acc9e30-f27f-436a-9dc4-213934d934b0","order_by":2,"name":"Zhitao Chen","email":"","orcid":"","institution":"Anhui Science and Technology University","correspondingAuthor":false,"prefix":"","firstName":"Zhitao","middleName":"","lastName":"Chen","suffix":""},{"id":511107569,"identity":"cc3d7c2f-8928-481e-af6d-7907b0deb552","order_by":3,"name":"Yang Wang","email":"","orcid":"","institution":"Anhui Science and Technology University","correspondingAuthor":false,"prefix":"","firstName":"Yang","middleName":"","lastName":"Wang","suffix":""},{"id":511107570,"identity":"dc46405d-a12a-4e7e-9089-baba3249620c","order_by":4,"name":"Ruiqi Wang","email":"","orcid":"","institution":"Anhui Science and Technology University","correspondingAuthor":false,"prefix":"","firstName":"Ruiqi","middleName":"","lastName":"Wang","suffix":""},{"id":511107571,"identity":"32e7cad1-02c4-43e2-bc3e-e9a3503ebe4b","order_by":5,"name":"Xinyu Xia","email":"","orcid":"","institution":"Anhui Science and Technology University","correspondingAuthor":false,"prefix":"","firstName":"Xinyu","middleName":"","lastName":"Xia","suffix":""},{"id":511107572,"identity":"d86053b4-5c9c-4e16-8f2d-81f5d196bf39","order_by":6,"name":"Lei Bai","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA8UlEQVRIie3SMWrDMBSA4ScE1iLq1bnFK4GmAZOeRRjUpUN6g2cCzeID+BiFXEDOo+0SyGpIh3jpbOgSqKFVA6Wb7bFQ/YPQoA9JSACh0B8MQeTOjzKWgrDFdDGG0JlM1iu6L5c2G0EA3Hmye6F33W4FDZGZYnLtkhXUJt+k6CQofnrsI/PCUFUiS1Ga1fQOXy9AW1v3HswZYo0HKRPz4MmbhERf9ZN9Q9x5EiVm/XGNLGiQ1H4X8ETriqYwhszLhqoCP2Wicros0GbR0F1m8W1zPHU2u2F1xFOXLmLFz73kp98XjMYs/274n4RCodD/7QtJxlKxVNJinwAAAABJRU5ErkJggg==","orcid":"","institution":"Anhui Science and Technology University","correspondingAuthor":true,"prefix":"","firstName":"Lei","middleName":"","lastName":"Bai","suffix":""},{"id":511107573,"identity":"a1a16f1a-dd0b-4f3d-837a-577d9314b9da","order_by":7,"name":"You Liu","email":"","orcid":"","institution":"Anhui Science and Technology University","correspondingAuthor":false,"prefix":"","firstName":"You","middleName":"","lastName":"Liu","suffix":""},{"id":511107574,"identity":"c20b4501-3a1e-41e6-87dd-250fe02767a2","order_by":8,"name":"Xuchun Wang","email":"","orcid":"","institution":"Anhui Science and Technology University","correspondingAuthor":false,"prefix":"","firstName":"Xuchun","middleName":"","lastName":"Wang","suffix":""},{"id":511107575,"identity":"e4b8455c-26db-4579-a6de-9d904dacb324","order_by":9,"name":"Yu Guo","email":"","orcid":"","institution":"Anhui Science and Technology University","correspondingAuthor":false,"prefix":"","firstName":"Yu","middleName":"","lastName":"Guo","suffix":""}],"badges":[],"createdAt":"2025-09-02 03:53:20","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-7513011/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-7513011/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":91095022,"identity":"7d77ecfb-1ba2-47ff-81c5-cdd47f6a70cb","added_by":"auto","created_at":"2025-09-11 13:56:05","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":49096,"visible":true,"origin":"","legend":"\u003cp\u003eXRD patterns of TiO\u003csub\u003e2\u003c/sub\u003e MRs and Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs with different silver content.\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-7513011/v1/ec9540e41cac715f2e681b0b.png"},{"id":91094218,"identity":"5c1bfd8b-9ba5-4d8b-9822-5e4d26fcc81e","added_by":"auto","created_at":"2025-09-11 13:48:05","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":540654,"visible":true,"origin":"","legend":"\u003cp\u003eHRTEM image of Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs-B (a) and corresponding crystalline lattice fringes (b), HAADF-STEM (c) image and EDX elemental mapping results of Ti (d) and Ag (e).\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-7513011/v1/4206a92e2e950cfb51e9f9b4.png"},{"id":91094242,"identity":"431c9a4c-5734-454b-8e40-8a052e92699a","added_by":"auto","created_at":"2025-09-11 13:48:06","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":46801,"visible":true,"origin":"","legend":"\u003cp\u003eXPS spectra of Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs-B (a), (b) Ag 3d peaks, (c) Ti 2p peaks, (d) O 1s peaks.\u0026nbsp;\u0026nbsp;\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-7513011/v1/8c06d29a05c5df548060e7b2.png"},{"id":91095016,"identity":"26fe7399-1f93-485d-b116-c422c509b4ca","added_by":"auto","created_at":"2025-09-11 13:56:05","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":45756,"visible":true,"origin":"","legend":"\u003cp\u003eTransient photocurrent response (a) and EIS spectroscopy (b) of TiO\u003csub\u003e2\u003c/sub\u003e MRs and Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs-B.\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-7513011/v1/949bf21cda3328fae03f1202.png"},{"id":91095031,"identity":"b8e58abd-945a-4293-b9da-70cd2bc9f06e","added_by":"auto","created_at":"2025-09-11 13:56:06","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":65991,"visible":true,"origin":"","legend":"\u003cp\u003eDegradation efficiency of MB over TiO\u003csub\u003e2\u003c/sub\u003e MRs and Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs with different silver content (a); the comparison of the apparent rate constants (\u003cem\u003ek\u003c/em\u003e) of the corresponding reaction(b); the comparative\u0026nbsp;experiment\u0026nbsp;of\u0026nbsp;different\u0026nbsp;dosage of catalysts (c); the independent runs for MB degradation over Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs-B (d).\u003c/p\u003e","description":"","filename":"5.png","url":"https://assets-eu.researchsquare.com/files/rs-7513011/v1/0f296951404ea8d74a19e1ee.png"},{"id":91095033,"identity":"08b1dd76-2312-44b8-80f0-55b1942c3dde","added_by":"auto","created_at":"2025-09-11 13:56:06","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":110792,"visible":true,"origin":"","legend":"\u003cp\u003eDegradation efficiency of RhB over TiO\u003csub\u003e2\u003c/sub\u003e MRs and Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs with different silver content (a); the comparison of the apparent rate constants (\u003cem\u003ek\u003c/em\u003e) of the corresponding reaction (b); the degradation efficiency at different temperatures (c); and the comparison of the apparent rate constants (\u003cem\u003ek\u003c/em\u003e) of the corresponding reaction(d).\u003c/p\u003e","description":"","filename":"6.png","url":"https://assets-eu.researchsquare.com/files/rs-7513011/v1/98006c7dcabc33e86aa37ec5.png"},{"id":91094200,"identity":"e62de539-7de1-4470-9fc9-2de06674c021","added_by":"auto","created_at":"2025-09-11 13:48:05","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":105528,"visible":true,"origin":"","legend":"\u003cp\u003eEffects of quenchers on the photodegradation of MB and RhB over Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs-B under UV light irradiation: (a) the quenching for MB degradation, (b) degradation percentages for MB in 20 min UV irradiation, (c) the quenching for RhB degradation, (d)degradation percentages for RhB in 20 min UV irradiation.\u003c/p\u003e","description":"","filename":"7.png","url":"https://assets-eu.researchsquare.com/files/rs-7513011/v1/a7b7f9819d7fca4ff8ad4d6f.png"},{"id":91095030,"identity":"9a209294-552b-4872-b494-9f04980b8544","added_by":"auto","created_at":"2025-09-11 13:56:06","extension":"png","order_by":8,"title":"Figure 8","display":"","copyAsset":false,"role":"figure","size":143194,"visible":true,"origin":"","legend":"\u003cp\u003eSchematic representation of possible degradation mechanism proposed for mixed phase Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs.\u003c/p\u003e","description":"","filename":"8.png","url":"https://assets-eu.researchsquare.com/files/rs-7513011/v1/7d3e68d74ef40f50b1e6cdb7.png"},{"id":91094207,"identity":"47036db5-148d-493a-a5d9-c6b429f35df7","added_by":"auto","created_at":"2025-09-11 13:48:05","extension":"png","order_by":9,"title":"Figure 9","display":"","copyAsset":false,"role":"figure","size":44684,"visible":true,"origin":"","legend":"\u003cp\u003eDegradation efficiency of RhB over TiO\u003csub\u003e2\u003c/sub\u003e MRs and Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs with different silver content (a); the comparison of the apparent rate constants (\u003cem\u003ek\u003c/em\u003e) of the corresponding reaction (b)\u003c/p\u003e","description":"","filename":"9.png","url":"https://assets-eu.researchsquare.com/files/rs-7513011/v1/eb56b0c73671f36fe27d2334.png"},{"id":91095040,"identity":"1bbecd39-af4a-4292-9584-ade515164398","added_by":"auto","created_at":"2025-09-11 13:56:07","extension":"png","order_by":10,"title":"Figure 10","display":"","copyAsset":false,"role":"figure","size":1423850,"visible":true,"origin":"","legend":"\u003cp\u003eInhibition zone for TiO\u003csub\u003e2\u003c/sub\u003e MRs(a), Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs-A (b), Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs-B(c) and Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs-C(d) against \u003cem\u003eS. aureus\u003c/em\u003e，the numbers 1, 2, and 3 denote independent experimental replicates\u003c/p\u003e","description":"","filename":"10.png","url":"https://assets-eu.researchsquare.com/files/rs-7513011/v1/6d8409871f05ce2fc5b9a55e.png"},{"id":91096925,"identity":"6152dd0f-981e-4bc7-9562-92968dfbe925","added_by":"auto","created_at":"2025-09-11 14:12:07","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":3737750,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-7513011/v1/56adfbfa-84c8-4633-86e6-8036ed2ac5dc.pdf"},{"id":91094230,"identity":"5876870c-a115-4b6f-9651-a849eeec05a6","added_by":"auto","created_at":"2025-09-11 13:48:06","extension":"docx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":680097,"visible":true,"origin":"","legend":"","description":"","filename":"Supportinginformation.docx","url":"https://assets-eu.researchsquare.com/files/rs-7513011/v1/02456ca6f75b38d530e78321.docx"},{"id":91094246,"identity":"072432ed-bc37-4fb4-ae5c-84f123162621","added_by":"auto","created_at":"2025-09-11 13:48:06","extension":"doc","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":23901184,"visible":true,"origin":"","legend":"","description":"","filename":"FulluncroppedGelsandBlotsimages.doc","url":"https://assets-eu.researchsquare.com/files/rs-7513011/v1/aa4fa0f97962b05fc4d3678c.doc"},{"id":91094247,"identity":"de86338d-4beb-451d-af5a-9a2a4a3a3def","added_by":"auto","created_at":"2025-09-11 13:48:06","extension":"png","order_by":3,"title":"","display":"","copyAsset":false,"role":"supplement","size":438741,"visible":true,"origin":"","legend":"","description":"","filename":"GraphicalAbstract.png","url":"https://assets-eu.researchsquare.com/files/rs-7513011/v1/4c3a6e6580b19fbe8cf97838.png"}],"financialInterests":"No competing interests reported.","formattedTitle":"\u003cp\u003eLow silver loaded biphase of TiO\u003csub\u003e2\u003c/sub\u003e microrods with TiO\u003csub\u003e2\u003c/sub\u003e(B)/anatase and their photocatalytic and antibacterial properties\u003c/p\u003e","fulltext":[{"header":"Highlights","content":"\u003cp\u003eA heterojunction was obtained by combining AgNPs with phase-tunable TiO\u003csub\u003e2\u003c/sub\u003e (B)/anatase MRs.\u003c/p\u003e\n\u003cp\u003eThe Ag-TiO\u003csub\u003e2\u003c/sub\u003e Schottky junction traps electrons, thus enhancing catalytic performance of RhB.\u003c/p\u003e\n\u003cp\u003eAg/TiO\u003csub\u003e2\u003c/sub\u003e MRs exhibit enhanced visible-light activity due to the surface plasmon resonance effect of AgNPs .\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eControlled Ag⁺ release from Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs provides dark antibacterial functionality.\u003c/p\u003e"},{"header":"1. Introduction","content":"\u003cp\u003eThe photocatalyst, titanium dioxide (TiO\u003csub\u003e2\u003c/sub\u003e), which has the advantages of high photocatalytic efficiency, low cost consumption, and non-toxicity \u003csup\u003e[\u003cspan additionalcitationids=\"CR2 CR3\" citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e]\u003c/sup\u003e, is considered to be one of the most promising semiconductor materials, and has been widely used in the field of photocatalytic degradation of pollutants\u003csup\u003e[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]\u003c/sup\u003e, water splitting\u003csup\u003e[\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e, \u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e]\u003c/sup\u003e, CO\u003csub\u003e2\u003c/sub\u003e reduction \u003csup\u003e[\u003cspan additionalcitationids=\"CR9\" citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e]\u003c/sup\u003e, photochromism \u003csup\u003e[\u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e]\u003c/sup\u003e and electrochromism \u003csup\u003e[\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e]\u003c/sup\u003e, solar cells\u003csup\u003e[\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e, \u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e]\u003c/sup\u003e, and ion batteries \u003csup\u003e[\u003cspan additionalcitationids=\"CR16\" citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e]\u003c/sup\u003e. TiO\u003csub\u003e2\u003c/sub\u003e exists in multiple polymorphic forms, such as rutile, anatase, brookite, and the bronze phase (TiO\u003csub\u003e2\u003c/sub\u003e(B)). Among these phases, anatase exhibits higher catalytic activity under UV irradiation due to the presence of numerous defects and oxygen vacancies as a electron shallow trap to delay charge recombination in the anatase TiO\u003csub\u003e2\u003c/sub\u003e lattice. TiO\u003csub\u003e2\u003c/sub\u003e(B) is usually synthesized through the transformation of layered titanate precursors\u003csup\u003e[\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e]\u003c/sup\u003e. It has a relatively open structure with free space and continuous channels, which gives it unique advantages in energy storage fields such as lithium-ion batteries\u003csup\u003e[\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e]\u003c/sup\u003e.\u003c/p\u003e\u003cp\u003eThe common methods for synthesizing TiO\u003csub\u003e2\u003c/sub\u003e include hydrothermal method\u003csup\u003e[\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e]\u003c/sup\u003e, sol-gel method\u003csup\u003e[\u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e]\u003c/sup\u003e, high-temperature solid state method\u003csup\u003e[\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e]\u003c/sup\u003e, microemulsion method\u003csup\u003e[\u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e]\u003c/sup\u003e, precipitation method\u003csup\u003e[\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e]\u003c/sup\u003e, electrospinning method\u003csup\u003e[\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e]\u003c/sup\u003e. It was well known that solid-state reaction is suitable for large-scale production and industrial production, with the advantages of stable reaction process and simple operation. By the method, layered metastable precursor K\u003csub\u003e2\u003c/sub\u003eTi\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e or K\u003csub\u003e2\u003c/sub\u003eTi\u003csub\u003e4\u003c/sub\u003eO\u003csub\u003e9\u003c/sub\u003e were synthesized\u003csup\u003e[\u003cspan additionalcitationids=\"CR27\" citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e]\u003c/sup\u003e firstly. The precursor was then hydrolyzed to form hydrated titanic acid (H\u003csub\u003e2\u003c/sub\u003eTi\u003csub\u003e4\u003c/sub\u003eO\u003csub\u003e9\u003c/sub\u003e\u0026middot;nH\u003csub\u003e2\u003c/sub\u003eO), which was subsequently calcined to yield TiO\u003csub\u003e2\u003c/sub\u003e. In this study, the layered titanate salt of K\u003csub\u003e2\u003c/sub\u003eTi\u003csub\u003e4\u003c/sub\u003eO\u003csub\u003e9\u003c/sub\u003e precursor was batch synthesized by Kneading-Drying-Calcination method (KDC) using titanic acid and K\u003csub\u003e2\u003c/sub\u003eCO\u003csub\u003e3\u003c/sub\u003e as raw materials\u003csup\u003e[\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e]\u003c/sup\u003e. Then by controlling the calcination temperature of H\u003csub\u003e2\u003c/sub\u003eTi\u003csub\u003e4\u003c/sub\u003eO\u003csub\u003e9\u003c/sub\u003e\u0026middot;nH\u003csub\u003e2\u003c/sub\u003eO, different crystalline phases of TiO\u003csub\u003e2\u003c/sub\u003e were obtained. As the temperature increased to 998.15K, the majority of the metastable phase TiO\u003csub\u003e2\u003c/sub\u003e(B) transformed into anatase, thus yielding a TiO\u003csub\u003e2\u003c/sub\u003e(B)/anatase type Ⅱ heterostructure\u003csup\u003e[\u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e]\u003c/sup\u003e, which will effectively promote the separation of electrons and holes.\u003c/p\u003e\u003cp\u003eMoreover, noble metal Ag loading is another measure to further reduce carrier recombination. Ag was dispersed on the surface of TiO\u003csub\u003e2\u003c/sub\u003e acting as electron traps, leading to the formation of the Schottky Barrier at the interface as an electronic one-way valve to suppress the rapid recombination of photogenerated electrons and holes. It was observed that loading an appropriate amount of Ag onto TiO\u003csub\u003e2\u003c/sub\u003e not only enhances its photocatalytic activity under UV radiation but also improves its photostability, maintaining higher catalytic degradation performance during repeated cycling tests. Besides, silver could also broaden the spectrum under visible light originated from the surface plasmon resonance effect (SPR)\u003csup\u003e[\u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e, \u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e31\u003c/span\u003e]\u003c/sup\u003e. Furthermore, based on the broad spectrum antibacterial performance of silver ions\u003csup\u003e[\u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e]\u003c/sup\u003e, the silver-loaded photocatalytic synergistic system can create a highly resistant bacterial environment\u003csup\u003e[\u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e]\u003c/sup\u003e, which can be applied in antibacterial coatings, indoor air purification, medical dressings, and surgical fabrics, etc.\u003c/p\u003e"},{"header":"2. Experimental section(Materials and methods)","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e\n \u003cp\u003e\u003cstrong\u003e2.1\u003c/strong\u003e\u003cstrong\u003e\u0026nbsp;\u003c/strong\u003e\u003cstrong\u003eMaterials\u003c/strong\u003e\u003c/p\u003e\n \u003cp\u003eThe starting materials, metatitanic acid (TiO(OH)\u003csub\u003e2\u003c/sub\u003e), anhydrous potassium caRhBonate (K\u003csub\u003e2\u003c/sub\u003eCO\u003csub\u003e3\u003c/sub\u003e)\u0026nbsp;were purchased from\u0026nbsp;Aladdin Chemicals Ltd,\u0026nbsp;China.\u0026nbsp;Silver nitrate (AgNO\u003csub\u003e3\u003c/sub\u003e),\u0026nbsp;absolute alcohol,\u0026nbsp;hydrochloric acid (37%),\u0026nbsp;methylene blue (MB) and Rhodamine B (RhB), were purchased from\u0026nbsp;Sinopharm Chemical Reagent Co, Ltd,\u0026nbsp;China.\u0026nbsp;The quenchers,\u0026nbsp;p-benzoquinone (BQ), tert-Butanol (tBA), and ethylenediaminetetraacetic acid disodium salt\u0026nbsp;dihydrate\u0026nbsp;(Na\u003csub\u003e2\u003c/sub\u003eEDTA) were purchased from Aladdin Chemicals Ltd, China.\u0026nbsp;\u003c/p\u003e\n \u003cp\u003eAll the experimental solutions were prepared with Millipore water (18 M\u0026Omega;.cm) collected from Elix Millipore system.\u003c/p\u003e\n \u003cp\u003e\u003cstrong\u003e2.2 K\u003csub\u003e2\u003c/sub\u003eTi\u003csub\u003e4\u003c/sub\u003eO\u003csub\u003e9\u0026nbsp;\u003c/sub\u003eprecursor\u003c/strong\u003e \u003cstrong\u003epreparation\u003c/strong\u003e\u003c/p\u003e\n \u003cp\u003ePure K\u003csub\u003e2\u003c/sub\u003eTi\u003csub\u003e4\u003c/sub\u003eO\u003csub\u003e9\u003c/sub\u003e precursors were prepared using the Kneading-Drying-Calcination (KDC) method. The chemical composition, specifically the TiO(OH)\u003csub\u003e2\u003c/sub\u003e/K\u003csub\u003e2\u003c/sub\u003eCO\u003csub\u003e3\u003c/sub\u003e molar ratio, was controlled at 3. The two reactants were mixed in a high-performance ball mill, using absolute ethanol as a grinding aid, and milled for 4 hours at a speed of 350 revolutions per minute (r/min). After drying at 333.15K, the resulting mixture was passed through an 80 mesh sieve. The mixture was then placed into a muffle furnace and sintered at 1273.15K for 1 hour to obtain the K\u003csub\u003e2\u003c/sub\u003eTi\u003csub\u003e4\u003c/sub\u003eO\u003csub\u003e9\u003c/sub\u003e precursor. The obtained precursor was ground through an 80 mesh sieve for subsequent use and characterization.\u003c/p\u003e\n \u003cp\u003e\u003cstrong\u003e2.3 TiO\u003csub\u003e2\u003c/sub\u003e microrods (TiO\u003csub\u003e2\u003c/sub\u003e\u0026nbsp;\u003c/strong\u003e\u003cstrong\u003eMRs\u003c/strong\u003e\u003cstrong\u003e) preparation\u003c/strong\u003e\u003cstrong\u003e\u0026nbsp;\u003c/strong\u003e\u003cstrong\u003e\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n \u003cp\u003eThe K\u003csub\u003e2\u003c/sub\u003eTi\u003csub\u003e4\u003c/sub\u003eO\u003csub\u003e9\u0026nbsp;\u003c/sub\u003eprecursor was hydrolyzed in acidic solution to obtain hydrated H\u003csub\u003e2\u003c/sub\u003eTi\u003csub\u003e4\u003c/sub\u003eO\u003csub\u003e9\u003c/sub\u003e powder after washing and drying. Then the resulting products was putted into a muffle furnace to sinter at 998.15K for 2 h to obtain mesoporous TiO\u003csub\u003e2\u003c/sub\u003e MRs with TiO\u003csub\u003e2\u003c/sub\u003e(B)/anatase heterojunctions.\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u003cstrong\u003e2.4 Ag/TiO\u003csub\u003e2\u003c/sub\u003e\u0026nbsp;\u003c/strong\u003e\u003cstrong\u003eheterostructured\u0026nbsp;\u003c/strong\u003e\u003cstrong\u003emicrorods (Ag/TiO\u003csub\u003e2\u003c/sub\u003e\u0026nbsp;\u003c/strong\u003e\u003cstrong\u003eMRs)\u0026nbsp;\u003c/strong\u003e\u003cstrong\u003epreparation\u003c/strong\u003e\u003c/p\u003e\n \u003cp\u003e400 mg of TiO\u003csub\u003e2\u003c/sub\u003e MRs were dispersed in 50 mL absolute ethanol, and treated ultrasonically for 30 min to obtain a milky white colored suspension. 8.5 mg silver nitrate (the atom ratio of silver to titanium is 1 to 100) was dispersed in 10 mL absolute ethanol, and added 5 \u0026mu;L ammonia to get a transparent solution. Then the prepared silver nitrate alcohol solution was mixed with the TiO\u003csub\u003e2\u003c/sub\u003e suspension by sonication and the mixture was heated to remove the absolute ethanol and collect powder. Finally, put the collected powder into a muffle furnace to calcine at 573.15K for 1 h. The obtained sample was denoted as Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs-A. The Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs with different silver contents were prepared using 25.5 mg (the atom ratio of silver to titanium is 3 to 100) and 42.5 mg (the atom ratio of silver to titanium is 5 to 100) of AgNO\u003csub\u003e3\u003c/sub\u003e (instead of 8.5 mg) and the corresponding samples were denoted as Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs-B and C, respectively.\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u003cstrong\u003e2.5 Structural characterization\u003c/strong\u003e\u003cstrong\u003e\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n \u003cp\u003eX-ray powder diffraction (XRD) patterns of TiO\u003csub\u003e2\u003c/sub\u003e MRs and the Ag/TiO\u003csub\u003e2\u003c/sub\u003e HNRs samples were obtained using a Shimadzu 6100 X-ray diffractometer (Japan) with a Cu K\u0026alpha; radiation with a wavelength (\u0026lambda;) of 0.15418 nm and at a scan rate (2\u0026theta;) of 10\u0026deg; min\u003csup\u003e\u0026ndash;1\u003c/sup\u003e. The morphologies of the samples were examined by field emission scanning electron microscopy (FE-SEM, TESCAN, MIRA3) , and a high-resolution transmission electron microscope (HRTEM, JEM-2100F, JEOL, Japan). UV-Visible absorption spectroscopy (ABs) and UV-Vis diffuse reflectance spectra (DRS) were carried out by using a Shimadzu UV-1800 spectrophotometer and Shimadzu UV-3600 spectrophotometer, respectively. The pore structure and surface area of the samples were performed by nitrogen adsorption and desorption method using advanced specific surface area and micropore analyzer (BSD-660M, China).\u0026nbsp;\u003c/p\u003e\n \u003cp\u003e\u003cstrong\u003e2.6 Optical Performance and photoelectrochemical performance Analysis\u003c/strong\u003e\u003c/p\u003e\n \u003cp\u003eThe separation ability of photo generated electron hole pairs was evaluated by photoluminescence spectroscopy (PL, Shimadzu, RF-6000 fluorescence spectrometer) with an excitation wavelength of 360 nm.\u0026nbsp;\u003c/p\u003e\n \u003cp\u003eTo obtain the optoelectronic properties of catalysts, the transient photocurrent was examined by electrochemical\u0026nbsp;workstation (CHI660E, China) and electrochemicalimpedance spectroscopy (EIS) was examined by electrochemical\u0026nbsp;workstation (Zahner-PP211, Germany). The transient photocurrent was performed in a conventional three-electrode cell using the indium tin oxide (ITO) substrate deposited the catalyst powder, a Pt plate and an Ag/AgCl electrode as working photoelectrode, the counter electrode and reference electrode, respectively. The photocurrent response of the samples was performed in a 0.5M Na\u003csub\u003e2\u003c/sub\u003eSO\u003csub\u003e4\u003c/sub\u003e aqueous solution under 0.5 volts voltage.\u003c/p\u003e\n \u003cp\u003e\u003cstrong\u003e2.\u003c/strong\u003e\u003cstrong\u003e7\u003c/strong\u003e\u003cstrong\u003e\u0026nbsp;\u003c/strong\u003e\u003cstrong\u003ePhotocatalytic tests\u003c/strong\u003e\u003c/p\u003e\n \u003cp\u003eThe photocatalytic activities of TiO\u003csub\u003e2\u003c/sub\u003e MRs and Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs with different silver contents were evaluated by degrading MB or RhB solution. Twenty milligrams of the photocatalyst and 100 mL of 10mg/L of the MB or RhB solution were added into a water-cooled photochemical reactor, and were stirred for 30 min to reach the desorption\u0026minus;absorption equilibrium in a dark box. Four milliliter aliquots were collected and then filtered with a micropore filter (0.45 \u0026mu;m) to remove the as-prepared photocatalysts, the filtrate was determined using UV\u0026ndash;Vis spectrophotometer and the concentration of solution was labeled as C\u003csub\u003e0\u003c/sub\u003e. A 500 W high-pressure mercury lamp was used to irradiate the suspension. The irradiance at the reaction liquid level, measured with an optical power density radiometer (CEL-NP2000-2A, China), was 7.98 mW/cm\u0026sup2; at the main wavelength of 365 nm.\u0026nbsp;At given time intervals, the concentration of solution was examined which was labeled as C\u003csub\u003et\u003c/sub\u003e. The following equation estimated the degradation efficiency.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec9\" class=\"Section2\"\u003e\n \u003cdiv id=\"Equa\" class=\"Equation\"\u003e\n \u003cdiv class=\"mathdisplay\" id=\"FileID_Equa\" name=\"EquationSource\"\u003e\u003cimg src=\"data:image/png;base64,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\" width=\"648\" height=\"94\"\u003e\u003c/div\u003e\n \u003c/div\u003e\n \u003cp\u003eThe degradation of RhB was conducted under a 500 W xenon lamp to verify the role of silver nanoparticles in expanding the visible light response range due to the SPR effect.\u0026nbsp;Thirty milligrams of the photocatalyst were added to 100 mL of a 10 mg/L RhB solution in a water-cooled photochemical reactor. The irradiance at the reaction liquid level, measured across the 290-800 nm wavelength range, was 18.60 mW/cm\u0026sup2;.\u003c/p\u003e\n \u003cp\u003e\u003cstrong\u003e2.\u003c/strong\u003e\u003cstrong\u003e7\u003c/strong\u003e\u003cstrong\u003e\u0026nbsp;Antibacterial\u0026nbsp;\u003c/strong\u003e\u003cstrong\u003etests\u0026nbsp;\u003c/strong\u003e\u003cstrong\u003ein the dark\u003c/strong\u003e\u003c/p\u003e\n \u003cp\u003eSterile filter paper disks\u0026nbsp;with a diameter of 1cm were\u0026nbsp;immersed in\u0026nbsp;2mg/mL suspension of antibacterial samples for 10 minutes.\u0026nbsp;0.1mL\u0026nbsp;of bacterial solution with a\u0026nbsp;\u003cem\u003eStaphylococcus aureus\u0026nbsp;\u003c/em\u003e(\u003cem\u003eS. aureus\u003c/em\u003e)\u0026nbsp;content of 10\u003csup\u003e4\u003c/sup\u003e CFU/mL was evenly coated onto the surface of Mueller Hinton agar plate culture medium. The above soaked filter paper disks were attached to the surface of the culture medium. Then the culture medium s with filter papers were placed in a 310.15K constant temperature incubator with a humidity of 80% for 20 hours. Finally\u0026zwnj;, the diameters of the inhibition zone were measured with a vernier caliper, accurated to 0.1 mm. The antibacterial experiment was repeated three times for each sample and the average value was obtained.\u0026nbsp;\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec10\" class=\"Section2\"\u003e\u003cbr\u003e\u003c/div\u003e"},{"header":"3. Results and discussion","content":"\u003cp\u003e\u003cstrong\u003e3.1\u0026nbsp;\u003c/strong\u003e\u003cstrong\u003eCharacterization analysis\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e\u003cem\u003e3.1.1\u0026nbsp;\u003c/em\u003e\u003cem\u003eXRD analysis\u003c/em\u003e\u003c/p\u003e\n\u003cp\u003eThe crystal structures and phase of TiO\u003csub\u003e2\u003c/sub\u003e MRs and Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs with different silver content were characterized by XRD, as shown in Figure 1. It can be observed that all the samples show a mixed phase of anatase and TiO\u003csub\u003e2\u003c/sub\u003e(B), and anatase is the main phase from the diffraction peaks .The\u003cstrong\u003e\u0026nbsp;\u003c/strong\u003epeaks at around 2\u0026theta; = 25.28\u0026deg;, 36.95\u0026deg;, 37.80\u0026deg;, 38.58\u0026deg;, 48.05\u0026deg;, 53.89\u0026deg; and 55.06\u0026deg;\u0026nbsp;are attributed to\u0026nbsp;anatase TiO\u003csub\u003e2\u003c/sub\u003e(JCPDS NO.21-1272),\u0026nbsp;corresponding to\u0026nbsp;(101),\u0026nbsp;(103),\u0026nbsp;(004),\u0026nbsp;(112),\u0026nbsp;(200),\u0026nbsp;(105)\u0026nbsp;and\u0026nbsp;(211)\u0026nbsp;crystal planes,\u0026nbsp;respectively. The weak peaks at around 2\u0026theta; = 24.93\u0026deg;, 28.61\u0026deg;\u0026nbsp;, 29.70\u0026deg;, 33.32\u0026deg;, 43.51\u0026deg;, 44.50\u0026deg;\u0026nbsp;and 48.53\u0026deg;\u0026nbsp;are attributed to metastable\u0026nbsp;TiO\u003csub\u003e2\u003c/sub\u003e(B) (JCPDS NO.46-1237), corresponding to\u0026nbsp;(110),\u0026nbsp;(002),\u0026nbsp;(40\u003cruby\u003e1\u003crp\u003e(\u003c/rp\u003e\n \u003crt\u003e\u0026mdash;\u003c/rt\u003e\n \u003crp\u003e)\u003c/rp\u003e\n \u003c/ruby\u003e),\u0026nbsp;(31\u003cruby\u003e1\u003crp\u003e(\u003c/rp\u003e\n \u003crt\u003e\u0026mdash;\u003c/rt\u003e\n \u003crp\u003e)\u003c/rp\u003e\n \u003c/ruby\u003e),\u0026nbsp;(003),\u0026nbsp;(60\u003cruby\u003e1\u003crp\u003e(\u003c/rp\u003e\n \u003crt\u003e\u0026mdash;\u003c/rt\u003e\n \u003crp\u003e)\u003c/rp\u003e\n \u003c/ruby\u003e)\u0026nbsp;and\u0026nbsp;(020)\u0026nbsp;crystal planes, respectively. It can be seen that the peak intensities of (110) and (020) crystal planes of metastable TiO\u003csub\u003e2\u003c/sub\u003e(B) decreased obviously with the increasing silver loading in Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs samples, meaning further transformation from metastable TiO\u003csub\u003e2\u003c/sub\u003e(B) phase to anatase phase.\u0026nbsp;It was revealed that the heterophase junction formed between\u0026nbsp;TiO\u003csub\u003e2\u003c/sub\u003e(B)\u0026nbsp;and anatase, which was the responsible for the high charge-separation efficiency in mixed phase photocatalysts.\u0026nbsp;Moreover, the crystal phase peak at 38.12\u0026deg; corresponding to the (111) crystal pane, which was\u0026nbsp;attributed to metallic Ag (JCPDS\u0026nbsp;NO.04-0783), was discovered in the patterns of Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs-B and C. Due to low silver loading, there was no occurrence of diffraction peak for elemental silver in Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs-A.\u003c/p\u003e\n\u003cp\u003e\u003cem\u003e3.1.2.\u003c/em\u003e\u003cem\u003e\u0026nbsp;\u003c/em\u003e\u003cem\u003eFE-\u003c/em\u003e\u003cem\u003eSEM and HRTEM-EDX analysis\u003c/em\u003e\u003c/p\u003e\n\u003cp\u003eSFig.1 shows FE-SEM images of TiO\u003csub\u003e2\u003c/sub\u003e MRs and Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs-B at lower magnification and higher magnification. The TiO\u003csub\u003e2\u003c/sub\u003e MRs sample (SFig.1a and 1c) exhibits an microrod morphology with a length shorter than 5 \u0026mu;m. The Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs-B (SFig.1b and 1d) has a similar morphology to that of pure TiO\u003csub\u003e2\u0026nbsp;\u003c/sub\u003eMRs. To further observe the morphology and structure of TiO\u003csub\u003e2\u003c/sub\u003e MRs and Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs, TEM image of Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs-B was recorded, as illustrated in Fig.2. As can be seen in Fig.2a, AgNPs were bound on the surface of TiO\u003csub\u003e2\u003c/sub\u003e MRs, indicating the formation of composite nanostructures. In Fig.2b, the HRTEM image revealed obvious lattice planes with spacings of ~0.351 and ~0.326 nm, which were correspond to the (101) plane of anatase TiO\u003csub\u003e2\u003c/sub\u003e and the (111) plane of metallic Ag\u003csup\u003e[\u003c/sup\u003e\u003csup\u003e34\u003c/sup\u003e\u003csup\u003e,\u003c/sup\u003e\u003csup\u003e35\u003c/sup\u003e\u003csup\u003e]\u003c/sup\u003e, respectively. In addition, the elemental mapping results (Fig.2c\u0026ndash;e) also demonstrated\u0026nbsp;the presence of low Ag on the TiO\u003csub\u003e2\u003c/sub\u003e surface. According to the above results, metallic Ag was successfully loaded on the TiO\u003csub\u003e2\u003c/sub\u003e surface to form Ag/TiO\u003csub\u003e2\u003c/sub\u003e heterojunction by the present facile strategy. The lattice stripes of the (110) plane of TiO\u003csub\u003e2\u003c/sub\u003e(B)\u0026nbsp;could not be identified\u0026nbsp;due to the small proportion of\u0026nbsp;TiO\u003csub\u003e2\u003c/sub\u003e(B) phase\u0026nbsp;or the similarity of the lattice stripes\u0026nbsp;of\u0026nbsp;the (101) plane of anatase TiO\u003csub\u003e2\u003c/sub\u003e and the (110) plane of TiO\u003csub\u003e2\u003c/sub\u003e(B).\u003c/p\u003e\n\u003cp\u003e\u003cem\u003e3.1.3. XPS analysis\u003c/em\u003e\u003c/p\u003e\n\u003cp\u003eThe successful loading of Ag on the TiO\u003csub\u003e2\u003c/sub\u003e surface was further investigated by XPS, which revealed the surface composition and their chemical states in the Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs. The XPS spectrum in Fig.3a displayed that the Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs-B sample was composed by Ti, O, C, and Ag. The Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs (Fig.3b) displayed two peaks with the binding energies of 368.4 eV, and 374.4 eV, indicating the presence of metallic silver (Ag\u003csup\u003e0\u003c/sup\u003e)\u003csup\u003e[\u003c/sup\u003e\u003csup\u003e36\u003c/sup\u003e\u003csup\u003e]\u003c/sup\u003e,\u0026nbsp;which\u0026nbsp;were\u0026nbsp;ascribed\u0026nbsp;to\u0026nbsp;Ag 3d 5/2, and Ag 3d 3/2 of Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs-B, respectively. As displayed in Fig.3c, the binding energies of 458.4 eV and 464.1 eV are attributed to Ti 2p 3/2 and Ti 2p 1/2 in Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs-B, respectively, confirming the presence of Ti (VI). As shown in Fig.3d, the peak at 529.8 and 531.4 eV can be attributed to the O 1s XPS profiles of all the samples.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cem\u003e3.1.4 UV\u003c/em\u003e\u003cem\u003e-\u003c/em\u003e\u003cem\u003eVis DRS analysis\u003c/em\u003e\u003c/p\u003e\n\u003cp\u003eTo further identify the successful loading of Ag, the ultraviolet-visible diffuse reflectance spectra (DRS) of all the samples were shown in SFig.2. It can be seen that the absorption edges of Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs showed red-shift slightly compared to bare TiO\u003csub\u003e2\u003c/sub\u003e MRs with the increase of Ag content as displayed in SFig.2a.The relationship between (F\u003cem\u003ehv\u003c/em\u003e)\u003csup\u003e1/2\u003c/sup\u003e and photon energy of samples was calculated by the Kubelka-Munk formula (F\u003cem\u003eh\u0026nu;\u003c/em\u003e)\u003csup\u003e1/n\u003c/sup\u003e=K/S=(1-R)\u003csup\u003e2\u003c/sup\u003e/2R= B(\u003cem\u003eh\u0026nu;\u003c/em\u003e-\u003cem\u003eE\u003c/em\u003e\u003csub\u003eg\u003c/sub\u003e), Where the K, S, R, \u003cem\u003eh\u003c/em\u003e, \u003cem\u003e\u0026nu;\u003c/em\u003e, and \u003cem\u003eE\u003c/em\u003e\u003csub\u003eg\u003c/sub\u003e represent absorption coefficient, the reflection coefficient, reflectivity (%), Planck\u0026apos;s constant, the frequency of the light, and the bandgap energy, n=1/2 for direct bandgap semiconductor, n=2 for indirect bandgap semiconductor. The results shown in SFig.2b indicate that the bandgap energy of TiO\u003csub\u003e2\u003c/sub\u003e MRs, Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs-A, Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs-B and Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs-C samples are 3.19 eV, 3.16 eV, 3.13 eV and 3.08 eV, respectively, suggesting that the loading of silver on the surface slightly reduced the bandgap width.\u003c/p\u003e\n\u003cp\u003e\u003cem\u003e3.1.5 N\u003csub\u003e2\u003c/sub\u003e adsorption\u003c/em\u003e\u003cem\u003e-\u003c/em\u003e\u003cem\u003edesorption analysis\u003c/em\u003e\u003c/p\u003e\n\u003cp\u003eAs shown in SFig.3 the N\u003csub\u003e2\u003c/sub\u003e adsorption‐desorption isotherms of TiO\u003csub\u003e2\u003c/sub\u003e MRs and Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs-B displayed type IV according to the BDDT (Deming and Teller) classification. When p/p\u003csup\u003e0\u003c/sup\u003e is in the range of 0.8 to 1, and hysteresis loops are similar to H3 type, indicating the presence of mesopores, which may be related to layered structure of K\u003csub\u003e2\u003c/sub\u003eTi\u003csub\u003e4\u003c/sub\u003eO\u003csub\u003e9\u0026nbsp;\u003c/sub\u003eprecursors\u003csup\u003e[\u003c/sup\u003e\u003csup\u003e19,37\u003c/sup\u003e\u003csup\u003e]\u003c/sup\u003e.\u0026nbsp;The pore size distribution curve (inset in\u0026nbsp;SFig.3) revealed that the prepared\u0026nbsp;TiO\u003csub\u003e2\u003c/sub\u003e MRs and Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs-B mainly contained mesopores and macropores.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eThe specific surface area, the pore volume and the average pore diameter of TiO\u003csub\u003e2\u003c/sub\u003e MRs are 16.2 m\u003csup\u003e2\u003c/sup\u003e/g, 0.066 cm\u003csup\u003e3\u003c/sup\u003e g\u003csup\u003e\u0026ndash;1\u003c/sup\u003e\u003csup\u003e\u0026nbsp;\u003c/sup\u003eand 16.42 nm, respectively.\u0026nbsp;Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs-B demonstrated the slightly lower specific surface area, the slightly higher pore volume, and the slightly higher average pore diameter: 13.8 m\u003csup\u003e2\u003c/sup\u003e /g, 0.069 cm\u003csup\u003e3\u003c/sup\u003e\u0026middot;g\u003csup\u003e\u0026ndash;1\u003c/sup\u003e, and 19.48 nm, respectively.\u0026nbsp;This result of\u0026nbsp;low\u0026nbsp;specific surface area is consistent well with the result of SEM displayed\u0026nbsp;microrods\u0026nbsp;morphology rather than\u0026nbsp;nanoscale.\u0026nbsp;Furthermore, in the\u0026nbsp;TiO\u003csub\u003e2\u003c/sub\u003e microrods preparation\u003cstrong\u003e\u0026nbsp;\u003c/strong\u003eprocess at\u0026nbsp;998.15K, only a small number of\u0026nbsp;slit pores\u0026nbsp;can be preserved, resulting in a small pore volume. After loading silver, the specific surface area slightly decreased, suggesting that a small amount of larger silver particles embedded in the slit increased the pore volume and pore size.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e3.\u003c/strong\u003e\u003cstrong\u003e2\u003c/strong\u003e\u003cstrong\u003e\u0026nbsp;Photoelectrochemical characterization\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe dynamic characteristics of photogenerated charge carriers in catalysts were explored through PL, photocurrent and EIS Analysis. It can be seen from SFig.4 that compared with TiO\u003csub\u003e2\u003c/sub\u003e MRs, the PL emission peak intensity of Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs-B is significantly lower than that of TiO\u003csub\u003e2\u003c/sub\u003e MRs, indicating that the loading of AgNPs reduces the recombination rate of photo generated electron-hole pairs. Under the same experimental conditions, the lifetime of charge carriers in Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs-B was extended and the catalytic performance was improved.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eIn order to furtherly investigate the effect of AgNPs on the photoelectric properties of TiO\u003csub\u003e2\u0026nbsp;\u003c/sub\u003emicrorods, the photocurrent of TiO\u003csub\u003e2\u003c/sub\u003e MRs and Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs-B were tested under 365 nm ultraviolet light irradiation. Fig. 4a shows that Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs-B exhibited a photocurrent density of 270 \u0026plusmn; 5 nA, which is 56% higher than that of TiO\u003csub\u003e2\u003c/sub\u003e MRs (173 \u0026plusmn; 5 nA). This improvement of charge separation could be attributed to electron trap effect of Ag and the formation of the Schottky junction, which is consistent with the PL measurements.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eAs shown in Fig. 4b, EIS \u003cstrong\u003emeasurements\u003c/strong\u003e for TiO\u003csub\u003e2\u003c/sub\u003e MRs and Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs-B were performed under \u003cstrong\u003e365 nm illumination\u003c/strong\u003e.\u0026nbsp;An equivalent circuit\u0026nbsp;diagram\u0026nbsp;with two semicircles\u0026nbsp;was\u0026nbsp;displayed\u0026nbsp;through Z-View fitting\u0026nbsp;(SFig.5).\u0026nbsp;Evidently,\u0026nbsp;the impedance diagram\u0026nbsp;showed that\u0026nbsp;the radius\u0026nbsp;of the arc\u0026nbsp;of\u0026nbsp;Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs-B (the charge-transfer resistance 9617 ohm) is smaller than TiO\u003csub\u003e2\u003c/sub\u003e MRs (32539 ohm), indicating that TiO\u003csub\u003e2\u003c/sub\u003e MRs loaded AgNPs composite are more conducive due to improving the transfer efficiency of charges at the electrode electrolyte interface and enhancing optoelectronic performance.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e3.\u003c/strong\u003e\u003cstrong\u003e3\u003c/strong\u003e\u003cstrong\u003e\u0026nbsp;Photocatalytic activity on\u0026nbsp;\u003c/strong\u003e\u003cstrong\u003eM\u003c/strong\u003e\u003cstrong\u003eB\u0026nbsp;\u003c/strong\u003e\u003cstrong\u003esolution\u0026nbsp;\u003c/strong\u003e\u003cstrong\u003eunder ultraviolet radiation\u003c/strong\u003e\u003cstrong\u003e\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe photodegradation efficiency of MB for\u0026nbsp;TiO\u003csub\u003e2\u003c/sub\u003e MRs and Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs with different silver content was displayed in Fig.5a. Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs-B showed the highest photocatalytic activity and the MB degradation efficiency was 93.11% within 30 min, which demonstrated an optimized amount of AgNPs on TiO\u003csub\u003e2\u003c/sub\u003e could promote the photocatalytic activity. Comparatively, the MB degradation efficiency was 81.34% for TiO\u003csub\u003e2\u003c/sub\u003e MRs. In spite of lower than that of Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs-B, it was still a higher degradation efficiency, which was attributed to the efficient charge separation of TiO\u003csub\u003e2\u003c/sub\u003e(B)/anatase heterostructures. However, the\u0026nbsp;degradation\u0026nbsp;efficiency\u0026nbsp;of 89.40%and 80.17% for Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs-A and Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs-C showed the insufficient or excessive loading of AgNPs were unfavorable to the photocatalytic process. It is speculated that the insufficient silver loading was unable to form an effective Schottky junction. However, the excessive silver loading led to the aggregation of silver particles, which not only shields the active sites but may also become recombination centers, thereby decreasing the activities. The degradation of MB obeyed pseudo-first order kinetics (shown in Fig.5b), which was indicated using ln(c\u003csub\u003e0\u003c/sub\u003e/c\u003csub\u003et\u003c/sub\u003e) = \u003cem\u003ek\u003c/em\u003et, where c\u003csub\u003e0\u0026nbsp;\u003c/sub\u003eand c\u003csub\u003et\u003c/sub\u003e are the initial and remaining MB, respectively; \u003cem\u003ek\u003c/em\u003e is the kinetics rate constant; and t is the UV light radiation time. Ag/TiO\u003csub\u003e2\u0026nbsp;\u003c/sub\u003eMRs-B had the largest reaction rate and\u0026nbsp;enhanced MB degradation by 1.60 times higher efficiency than TiO\u003csub\u003e2\u003c/sub\u003e MRs (shown in STable 1).\u003c/p\u003e\n\u003cp\u003eThe catalytic efficiency of both TiO\u003csub\u003e2\u003c/sub\u003e MRs and Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs-B composite increased as the usage of catalysts increased from 20 mg to 30 mg, especially, the MB degradation efficiency for Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs-B composite increased from 84.52% to 99.80% in 20 min (shown in Fig.5c). Fig.5d displayed the result of the stability test for Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs-B through four cycles of use (20mg, 30min). The MB degradation efficiency decreased lightly and yet remained 91.00% for the fourth cycle, which confirms that Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs-B have a good photostability.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e3.\u003c/strong\u003e\u003cstrong\u003e4\u003c/strong\u003e\u003cstrong\u003e\u0026nbsp;Photocatalytic activity on\u0026nbsp;\u003c/strong\u003e\u003cstrong\u003eRhB\u003c/strong\u003e\u003cstrong\u003e\u0026nbsp;\u003c/strong\u003e\u003cstrong\u003esolution\u0026nbsp;\u003c/strong\u003e\u003cstrong\u003eunder ultraviolet radiation\u0026nbsp;\u003c/strong\u003e\u003cstrong\u003eand the calculation of activation energy E\u003csub\u003ea\u003c/sub\u003e\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe degradation efficiency of RhB was shown in Fig.6a. The degradation efficiency of RhB using\u0026nbsp;TiO\u003csub\u003e2\u003c/sub\u003e MRs reached only 50.94% within 30 minutes, which was significantly lower than the 81.34% efficiency observed for MB under identical conditions. It was inferred that there was a lack of strong electrostatic adsorption between the negatively charged TiO\u003csub\u003e2\u003c/sub\u003e surface and the electrically neutral RhB molecules at neutral pH. And the highly stable conjugated xanthene chromophore structure of RhB was another reason for the low degradation rate. Nevertheless, loading with AgNPs significantly enhanced the RhB degradation efficiency of the TiO\u003csub\u003e2\u003c/sub\u003e MRs, which has already been proved that the RhB degradation efficiency reached 93.17%, 96.71%, and 89.74% for Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs-A, B, and C, respectively. The degradation rate of RhB obeyed pseudo-first order kinetics as well (shown in Fig.6b). It was found that the apparent rate constant of RhB with Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs-A, Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs-B and Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs-C was approximately 0.08949 min\u003csup\u003e-1\u003c/sup\u003e,\u0026nbsp;0.11382 min\u003csup\u003e-1\u003c/sup\u003e, and\u0026nbsp;0.07529\u0026nbsp;min\u003csup\u003e-1\u003c/sup\u003e,\u0026nbsp;which were 3.77, 4.80 and 3.18 times higher\u0026nbsp;than that of TiO\u003csub\u003e2\u003c/sub\u003e MRs , respectively (shown in STable 2). Ag/TiO\u003csub\u003e2\u0026nbsp;\u003c/sub\u003eMRs-B\u0026nbsp;enhanced MB and RhB degradation by 1.60 times and 4.80 times higher efficiency than TiO\u003csub\u003e2\u003c/sub\u003e MRs, which demonstrated that there were differences in the degradation pathways of MB and RhB and the AgNPs introduced new catalytic sites that prominently altered and accelerated the degradation pathway of RhB.\u003c/p\u003e\n\u003cp\u003eThe degradation efficiency and reaction rate at 285.15K, 296.15K and 308.15K were examined (as shown in Fig.6c and 6d), and it was shown that photocatalytic degradation rate constants have been increased with the rising of temperature. The RhB degradation efficiency was 46.63%, 66.07%, 80.85% in 10min, respectively. \u0026nbsp;Based on the photocatalytic reaction rates at different temperatures combined with Arrhenius equation, the apparent activation energy (E\u003csub\u003ea\u003c/sub\u003e)\u0026nbsp;of catalyst was estimated\u0026nbsp;as\u0026nbsp;22.73 KJ/mol. (STable 3).\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e3.\u003c/strong\u003e\u003cstrong\u003e5\u003c/strong\u003e\u003cstrong\u003e\u0026nbsp;\u003c/strong\u003e\u003cstrong\u003eMechanism\u0026nbsp;\u003c/strong\u003e\u003cstrong\u003eof photodegradation\u0026nbsp;\u003c/strong\u003e\u003cstrong\u003edye under ultraviolet radiation\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eTo understand the photocatalytic mechanism of degradation organic dyes, the scavenging experiments were carried out to investigate the radicals during the reaction. The quenchers, including ethylenediaminetetraacetic acid disodium salt (Na\u003csub\u003e2\u003c/sub\u003eEDTA), p-benzoquinone (BQ) and tert-Butanol (tBA) were employed as h\u003csup\u003e+\u003c/sup\u003e, \u0026bull;O\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e-\u003c/sup\u003e and HO\u0026bull; scavengers, respectively. As Fig.7 shown, with increasing scavenger addition dose, it was observed that a higher quenching effect on the dye degradation over Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs-B (30mg) was achieved, moreover, the addition of scavengers had a greater impact on RhB solution than on MB solution. For MB solution (Fig.7a and 7b) as the addition doses of Na\u003csub\u003e2\u003c/sub\u003eEDTA were 0.5 mmol/L and 1 mmol/L, the addition doses of BQ were 0.5 mmol/L and 1 mmol/L, the addition doses of tBA were 10 mmol/L and 50 mmol/L, the degradation efficiency in 20 min decreased from 99.80% to 81.23% and 69.19%, to 82.20% and 67.86%, to 92.29% and 83.52%, respectively. Comparatively, for RhB solution (Fig.7c\u0026nbsp;and 7d) at the same condition, the degradation efficiency decreased from 99.81% to 64.60% and 24.31% , to 49.55% and 34.41%, to 59.90% and 48.53%, respectively. The results suggested that active species\u0026nbsp;h\u003csup\u003e+\u003c/sup\u003e,\u0026nbsp;\u0026bull;O\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e-\u003c/sup\u003e,\u0026nbsp;and\u0026nbsp;HO\u0026bull;\u0026nbsp;played a crucial role in the reaction mechanism for RhB degradation. The reason is that the\u0026nbsp;highly stable conjugated xanthene chromophore structure\u0026nbsp;of RhB\u0026nbsp;is more easily attacked and destroyed by\u0026nbsp;h\u003csup\u003e+\u0026nbsp;\u003c/sup\u003eand\u0026nbsp;HO\u0026bull;. The hinderance effect of electronic flow on Schottky junction between Ag-TiO\u003csub\u003e2\u003c/sub\u003e interface effectively separates photogenerated charges, thus significantly increase the number of h\u003csup\u003e+\u0026nbsp;\u003c/sup\u003eavailable for oxidation of RhB.\u0026nbsp;While the degradation pathway of MB,\u0026nbsp;in addition to the traditional semiconductor photocatalytic mechanism, also includes\u0026nbsp;the predominant dye self-sensitization mechanism, where the source of electrons is the dye molecules themselves and is significantly different from the process of electrons generated by photoexcitation of TiO\u003csub\u003e2\u003c/sub\u003e.\u003c/p\u003e\n\u003cp\u003eThe possible photocatalytic mechanism of Ag/TiO\u003csub\u003e2\u003c/sub\u003e HMRs for MB and RhB degradation was proposed and shown in Fig.8. The photocatalytic efficiency of a semiconductor is primarily governed by its energy band structure, including the band gap value and the positions of the valence band edge (VBE) and conduction band edge (CBE). The band gap energies of anatase and TiO\u003csub\u003e2\u003c/sub\u003e(B)\u0026nbsp;are\u0026nbsp;3.20~3.23eV\u0026nbsp;and\u0026nbsp;3.09~3.22eV\u003csup\u003e[\u003c/sup\u003e\u003csup\u003e38\u003c/sup\u003e\u003csup\u003e]\u003c/sup\u003e, sharing\u0026nbsp;a similar band gap,\u0026nbsp;but\u0026nbsp;they exhibit distinct band edge alignments\u0026nbsp;that\u0026nbsp;the conduction band bottom\u0026nbsp;and valence band top\u0026nbsp;of anatase lie at a lower energy level than those\u0026nbsp;of\u0026nbsp;TiO\u003csub\u003e2\u003c/sub\u003e(B)\u003csup\u003e[\u003c/sup\u003e\u003csup\u003e39,40\u003c/sup\u003e\u003csup\u003e]\u003c/sup\u003e.When a\u0026nbsp;TiO\u003csub\u003e2\u003c/sub\u003e(B)/anatase mixed-phase system\u0026nbsp;is formed, a heterophase\u0026nbsp;junction\u0026nbsp;(a typical Type-II heterojunction)\u0026nbsp;is\u0026nbsp;formed\u0026nbsp;at the interface. Meanwhile,\u0026nbsp;an internal electric field\u0026nbsp;occurs\u0026nbsp;inducing from the difference in band edge positions, which drives photogenerated electrons toward one phase and holes toward the other,\u0026nbsp;thus\u0026nbsp;resulting in highly efficient charge separation.\u0026nbsp;Under UV irradiation,\u0026nbsp;when\u0026nbsp;photogenerated electrons transfer from the conduction band of\u0026nbsp;TiO\u003csub\u003e2\u003c/sub\u003e(B) to the slightly lower conduction band of anatase,\u0026nbsp;accumulating\u0026nbsp;within the anatase phase,\u0026nbsp;photogenerated\u0026nbsp;holes migrate from the valence band of anatase to that of\u0026nbsp;TiO\u003csub\u003e2\u003c/sub\u003e(B), accumulating\u0026nbsp;on the\u0026nbsp;TiO\u003csub\u003e2\u003c/sub\u003e(B) side. Furthermore, low Ag loading dramatically improved the carriers separation efficiency via electron transfer process from the conduction band of TiO\u003csub\u003e2\u003c/sub\u003e to the adjacent AgNPs, which possess a higher work function. Thus, in Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs, a Schottky barrier at the metal-semiconductor interface was formed, which acted as an efficient electron trap, suppressing carrier recombination and enabling electron transfer to molecular oxygen (O\u003csub\u003e2\u003c/sub\u003e) to form superoxide anion radicals (\u0026middot;O\u003csub\u003e2\u003c/sub\u003e⁻).\u0026nbsp;As a consequence,\u0026nbsp;this composite significantly facilitates interfacial charge transfer and\u0026nbsp;reduces\u0026nbsp;the recombination of electron-hole pairs.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e3.\u003c/strong\u003e\u003cstrong\u003e6 Expanding spectra and antibacterial effect of AgNPs\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eSimilarly, AgNPs in the composite not only act as traps to capture electrons, but also play an extended spectral role under a xenon lamp simulating sunlight.\u0026nbsp;The\u0026nbsp;RhB\u0026nbsp;degradation reaction obeyed pseudo-first order kinetics as well.\u0026nbsp;When RhB solution was irradiated for 150 minutes,\u0026nbsp;the RhB degradation efficiency was 88.29%, 89.57%, 94.80% and 93.5% for\u0026nbsp;TiO\u003csub\u003e2\u003c/sub\u003e MRs, Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs-A, Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs-B and Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs-C, respectively(as shown in Fig.9 ). The slight enhancement of catalytic activity of silver loaded samples indicated that elemental silver extended the response range from ultraviolet to visible light through SPR effect. Invariably, the Ag/TiO\u003csub\u003e2\u0026nbsp;\u003c/sub\u003eMRs-B \u003cstrong\u003eexhibited the strongest performance\u003c/strong\u003e in RhB degradation \u003cstrong\u003eunder\u0026nbsp;\u003c/strong\u003esimulated sunlight\u003cstrong\u003e,\u0026nbsp;\u003c/strong\u003ethe apparent rate constant were 1.36 times higher\u0026nbsp;than that TiO\u003csub\u003e2\u003c/sub\u003e MRs than that of TiO\u003csub\u003e2\u003c/sub\u003e MRs ( STable 4 ).\u003c/p\u003e\n\u003cp\u003eThe antibacterial activity of TiO\u003csub\u003e2\u003c/sub\u003e MRs and Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs with different silver content against \u003cem\u003eS. aureus\u003c/em\u003e\u003cem\u003e\u0026nbsp;\u003c/em\u003ein the dark was evaluated\u0026nbsp;by\u0026nbsp;using the disk diffusion method, as shown in\u0026nbsp;Fig.10.\u0026nbsp;Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs-B and Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs-C showed \u003cstrong\u003eweak inhibition\u003c/strong\u003e with a zone diameter of 12.5 mm and 12.2 mm, while TiO\u003csub\u003e2\u003c/sub\u003e MRs and Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs-A exhibited \u003cstrong\u003eno inhibition\u003c/strong\u003e\u003cstrong\u003e，\u003c/strong\u003e\u003cstrong\u003eas shown in\u0026nbsp;\u003c/strong\u003eFig.10 and STable 5. AgNPs inhibit bacterial growth in the dark through direct contact mechanisms, including disruption of cell membrane integrity and interference with DNA replication. When AgNPs coexist with titanium dioxide, the composite exhibits a synergistic effect, which could be verified by subsequent experiments.\u003c/p\u003e"},{"header":"4. Conclusions","content":"\u003cp\u003eIn this work, a biphase composite TiO\u003csub\u003e2\u003c/sub\u003e MRs and optimized silver loading Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs exhibited significantly enhanced activity under both UV and simulated solar light irradiation. Photoelectrochemical and PL characterization further confirmed the effect of AgNPs on the migration, transportation, and recombination processes of photogenerated charge carriers. The degradation pathways of RhB and MB over Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs were inferred by the scavenging experiments. The inhibition zone experiment in the dark confirmed that Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs functions as a silver ion reservoir. This article offered a valuable strategy for catalyst design in the batch synthesis of TiO\u003csub\u003e2\u003c/sub\u003e MRs and their application in dye degradation. The findings of this work was expected to provide an efficient and sustainable solution to address environmental pollution and public health issues.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eFunding\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThis work was supported by Anhui Province Applied Peak Cultivation Discipline (No. XK-XJGF005) and Anhui\u0026nbsp;Province\u0026nbsp;Key\u0026nbsp;Research\u0026nbsp;and\u0026nbsp;Development\u0026nbsp;Program ( No. 202304a05020085).\u003cstrong\u003e\u0026nbsp; \u0026nbsp;\u003c/strong\u003e\u003cstrong\u003e\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eConflict of interest \u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eNo conflict of interest exits in the submission of this manuscript, and all the authors listed have approved the manuscript that is enclosed.\u003cstrong\u003e\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAuthor contributions\u0026nbsp;\u003c/strong\u003eZD, ZZ, ZC, YW, RW and XX performed the experiment, ZD wrote the original draft. LB, YL, XW, and YG supervised, reviewed, and edited, and provided the resources.\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n \u003cli\u003eKhan SUM, Al-Shahry M, Ingler WB (2003) Efficient Photochemical Water Splitting by a Chemically Modified n-TiO\u003csub\u003e2\u003c/sub\u003e. Science 297(5590):2243-2245. https://doi.org/10.1126/science.1075035\u003c/li\u003e\n \u003cli\u003eBasavarajappa PS, Patil SB, Ganganagappa N, Reddy KR, Raghu AV, Reddy CV (2020) Recent progress in metal-doped TiO\u003csub\u003e2\u003c/sub\u003e, non-metal doped/codoped TiO\u003csub\u003e2\u003c/sub\u003e and TiO\u003csub\u003e2\u003c/sub\u003e nanostructured hybrids for enhanced photocatalysis. Int J Hydrogen Energ 45(13):7764-7778. https://doi.org/10.1016/j.ijhydene.2019.07.241\u003c/li\u003e\n \u003cli\u003eRasouli K, Alamdari A, Sabbaghi S (2023) Ultrasonic-assisted synthesis of \u0026alpha;-Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e@TiO\u003csub\u003e2\u003c/sub\u003e photocatalyst: Optimization of effective factors in the fabrication of\u0026ensp;photocatalyst\u0026ensp;and removal of non-biodegradable cefixime via response surface methodology-central composite design. Sep Purif Technol 307:122799. https://doi.org/10.1016/j.seppur.2022.122799\u003c/li\u003e\n \u003cli\u003eHamza ZA, Dawood JJ, Jabbar MA (2024) Review of TiO\u003csub\u003e2\u003c/sub\u003e as Desulfurization Catalyst for Petroleum. Catalysts 14(6):381-400. https://doi.org/10.3390/catal14060381\u003c/li\u003e\n \u003cli\u003eSathishkumar K, Sowmiya K, Arul Pragasan L, Rajagopal R, Sathya R, Ragupathy S, Krishnakumar M, Reddy VRM (2022) Enhanced photocatalytic degradation of organic pollutants by Ag-TiO\u003csub\u003e2\u003c/sub\u003e loaded cassava stem activated caRhBon under sunlight irradiation.Chemosphere 302:134844. https://doi.org/10.1016/j.chemosphere.2022.134844\u003c/li\u003e\n \u003cli\u003eBackus EHG, Hosseinpour S, Ramanan C, Sun S, Schlegel SJ, Zelenka M, Jia XY, Gebhard M, Devi A, Wang HI, Bonn M (2024) Ultrafast Surface-specific spectroscopy of water at a photoexcited TiO\u003csub\u003e2\u003c/sub\u003e model water-splitting photocatalyst. Angew Chem Int Ed 63 (8):e202312123. https://doi.org/10.1002/anie.202312123\u003c/li\u003e\n \u003cli\u003eNguyen CQQ, Zhu GP, Jia DM, Ye W, Wang YK, Wang J, Ting T, Xu FC, Gan J, Li WH, Gao P (2021) Built-in electric field for photocatalytic overall water splitting through a TiO\u003csub\u003e2\u003c/sub\u003e/BiOBr P-N heterojunction. Nanoscale 13 (8):4496-4504. https://doi.org/10.1039/d0nr08928a\u003c/li\u003e\n \u003cli\u003eAhmadi M, Alavi SM, Larimi A (2023) Pt\u0026ndash;Cu@Bi\u003csub\u003e2\u003c/sub\u003eMoO\u003csub\u003e6\u003c/sub\u003e/TiO\u003csub\u003e2\u003c/sub\u003e Photocatalyst\u0026ensp;for CO\u003csub\u003e2\u003c/sub\u003e Reduction.Inorg.Chem 62 (49):20372-20389. https://doi.org/10.1021/acs.inorgchem.3c03372\u003c/li\u003e\n \u003cli\u003eNguyen TP, Dang LTN , Nguyen VH, Le TH, Vo DVN，Trinh QT, Bae SR, Sang YC, Kim SY, Le QV (2020) Recent Advances in TiO\u003csub\u003e2\u003c/sub\u003e-Based Photocatalysts for Reduction of CO\u003csub\u003e2\u003c/sub\u003e to Fuels. Nanomaterials 10(2):337. https://doi.org/10.3390/NANO1002033\u003c/li\u003e\n \u003cli\u003eFiroozabadi SR, Khosravi-Nikou MR, Shariati A (2023) CO\u003csub\u003e2\u0026nbsp;\u003c/sub\u003ephotoreduction\u0026ensp;using\u0026ensp;TiO\u003csub\u003e2\u003c/sub\u003e\u0026ensp;nanoflower /UiO-66 composite under UV light irradiation. \u003cem\u003eJ Environ Chem Eng\u003c/em\u003e 11 (5):110978. https://doi.org/10.1016/j.jece.2023.110978\u003c/li\u003e\n \u003cli\u003eBelhomme L, Duttine M, Labrug\u0026egrave;re C, Coicaud E, Rougier A, Penin N, Dandre A,Ravaine S,Gaudon M (2024) Investigation of the Photochromism of WO\u003csub\u003e3\u003c/sub\u003e,TiO\u003csub\u003e2\u003c/sub\u003e, and Composite WO\u003csub\u003e3\u003c/sub\u003e-TiO\u003csub\u003e2\u003c/sub\u003e Nanoparticles. Inorg Chem 63(21):10079-10091. https://doi.org/10.1021/acs.inorgchem.4c01379\u003c/li\u003e\n \u003cli\u003eSoltani S, Ardyanian M, Shahidi MM (2024) Enhancement of electrochromic efficiency of TiO\u003csub\u003e2\u003c/sub\u003e nanorods. Opt mater 152:115484. https://doi.org/10.1016/j.optmat.2024.115484\u003c/li\u003e\n \u003cli\u003eNivethitha R, Neha P, Aarthi K, Jeyadheepan K, Gandhi S (2025) Enhancing the efficiency of dye sensitized solar cells using TiO\u003csub\u003e2\u003c/sub\u003e/ Sr\u003csub\u003e1-x\u003c/sub\u003eCaSiO\u003csub\u003e4\u003c/sub\u003e:\u003csub\u003ex\u003c/sub\u003eTb\u003csup\u003e3+\u003c/sup\u003e nanocomposite as a photoelectrode modifier. Journal of power sources 641:236877. https://doi.org/10.1016/j.jpowsour.2025.236877\u003c/li\u003e\n \u003cli\u003e14. Wen Z, Liang C, Li S, Wang G, He B, Gu H, Xie J, Pan H, Su Z, Gao X, Hong G, Chen S (2024) High-Quality van der Waals Epitaxial CsPbBr\u003csub\u003e3\u003c/sub\u003e Film Grown on Monolayer Graphene Covered TiO\u003csub\u003e2\u003c/sub\u003e for High-Performance Solar Cells. Energy \u0026amp; Environmental Materials 7(4):12680. https://doi.org/10.1002/eem2.12680\u003c/li\u003e\n \u003cli\u003e15. Wang X, Cheng W, Hu J, Yu H, Kong X, Uemura S, Kusunose T, Feng Q (2022) Topochemical synthesis of Mn\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/TiO\u003csub\u003e2\u003c/sub\u003e and MnTiO\u003csub\u003e3\u003c/sub\u003e/TiO\u003csub\u003e2\u003c/sub\u003e nanocomposites as lithium-ion battery anodes with fast Li\u003csup\u003e+\u003c/sup\u003e migration and giant pseudocapacitance via the mesocrystalline effect, Nanoscale 14(37):13696-13710. https://doi.org/ 10.1039/d2nr03516b\u003c/li\u003e\n \u003cli\u003eRen Y, Liu Z, Pourpoint F, Armstrong AR, Grey CP, Bruce PG (2012) Nanoparticulate TiO\u003csub\u003e2\u003c/sub\u003e(B): an anode for lithium-ion batteries. Angew Chem Int Ed 51(9):2164-2167. https://doi.org/10.1002/anie.201108300\u003c/li\u003e\n \u003cli\u003eWang SH, Zhu YY, Sun XJ, An SL, Cui JL, Zhang YQ, He WX (2021) Microwave synthesis of N-doped modified graphene/mixed crystal phases TiO\u003csub\u003e2\u003c/sub\u003e composites for Na-ion batteries. Colloid Surface A 615:126276. https://doi.org/10.1016/j.colsurfa.2021.126276\u003c/li\u003e\n \u003cli\u003eFeist TP, Davies PK (1992) The soft chemical synthesis of TiO\u003csub\u003e2\u003c/sub\u003e (B) from layered titanates. \u003cstrong\u003eJ\u003c/strong\u003e\u003cstrong\u003eSolid\u003c/strong\u003e\u003cstrong\u003eState Chem\u003c/strong\u003e\u0026zwnj;\u0026zwnj;101(2):275-295. https://doi.org/10.1016/0022-4596(92)90184-w\u003c/li\u003e\n \u003cli\u003eWei H, Rodriguez EF, Hollenkamp AF, Bhatt AI, Chen DH, Caruso RA (2017) High reversible pseudocapacity in mesoporous Yolk-shell anatase TiO\u003csub\u003e2\u003c/sub\u003e/TiO\u003csub\u003e2\u003c/sub\u003e(B) microspheres used as anodes for Li-ion batteries. Adv Funct Mater 27(46):1703270. https://doi.org/10.1002/adfm.201703270\u003c/li\u003e\n \u003cli\u003eZhang E, Pan Y, Lu T, Zhu Y, Dai W (2020) Novel synthesis of S‑doped anatase TiO\u003csub\u003e2\u003c/sub\u003e via hydrothermal reaction of Cu\u0026ndash;Ti amorphous alloy. Applied Physics A 126:606. https://doi.org/10.1007/s00339-020-03790-1\u003c/li\u003e\n \u003cli\u003eAnsari F, SheibaniS, Caudillo-Flores U. et al. Effect of TiO\u003csub\u003e2\u003c/sub\u003e nanoparticle loading by sol\u0026ndash;gel method on the gas-phase photocatalytic activity of CuxO\u0026ndash;TiO2 nanocomposite. J Sol-Gel Sci Technol 96, 464\u0026ndash;479 (2020). https://doi.org/10.1007/s10971-020-05388-8\u003c/li\u003e\n \u003cli\u003eWang XY, Xie KY, Li J, Lai YQ, Zhang ZA, Liu YX (2011) Synthesis and electrochemical performance of TiO\u003csub\u003e2\u003c/sub\u003e-B as anode material. \u003cem\u003eJ Cent South Univ\u0026nbsp;\u003c/em\u003e18(2):406-410. https://doi.org/10.1007/s11771-011-0711-9\u003c/li\u003e\n \u003cli\u003eZielińska A, Kowalska E, Sobczak JW, Łącka I, Gazda M, Ohtani B, Hupka J, Zaleska A (2010) Silver-doped TiO\u003csub\u003e2\u003c/sub\u003e prepared by microemulsion method: Surface properties, bio- and photoactivity. Sep Purif Technol 72(3):309-318. https://doi.org/10.1016/j.seppur.2010.03.002\u003c/li\u003e\n \u003cli\u003eYin S, Ihara K, Aita Y, Komatsu M, Sato T (2006) Visible-Light Induced Photocatalytic Activity of TiO\u003csub\u003e2-\u003c/sub\u003exAy (A=N,S) Prepared by Precipitation Route. \u003cem\u003eJ Photoch Photobio A\u0026nbsp;\u003c/em\u003e179(1-2):105-114. https://doi.org/10.1016/j.jphotochem.2005.08.001\u003c/li\u003e\n \u003cli\u003eWelna DT, Bender JD, Wei XL, Sneddon LG, Allcock HR (2005) Preparation of Boron-CaRhBide/CaRhBon Nanofibers from a Poly(noRhBornenyldecaborane) Single-Source Precursor via Electrostatic Spinning. \u003cstrong\u003eAdv\u003c/strong\u003e\u003cstrong\u003eMater\u003c/strong\u003e17(7):859-862. https://doi.org/10.1002/adma.200401257\u003c/li\u003e\n \u003cli\u003eHe M, Lu XH, Feng X, Yu L, Yang ZH (2004) A simple approach to mesoporous fibrous titania from potassium dititanate. \u003cem\u003eChem Commun\u0026nbsp;\u003c/em\u003e10(19):2202-2203. https://doi.org/10.1039/b408609k\u003c/li\u003e\n \u003cli\u003eBao NZ, Feng X, Lu XH, Shen LM, Yanagisawa K (2004) Low-temperature controllable calcination syntheses of potassium dititanate. Aiche J 50(7):1568-1577. https://doi.org/10.1002/aic.10167\u003c/li\u003e\n \u003cli\u003eZhu YH, Li W, Zhou YX, Lu XH, Feng X, Yang ZH (2009) Low-Temperature CO Oxidation of Gold Catalysts Loaded on Mesoporous TiO\u003csub\u003e2\u003c/sub\u003e Whisker Derived from Potassium Dititanate. Catal Lett 127(3):406-410. https://doi.org/10.1007/s10562-008-9710-3\u003c/li\u003e\n \u003cli\u003eSarkar D, Chattopadhyay KK(2014)Branch density-controlled synthesis of hierarchical TiO\u003csub\u003e2\u003c/sub\u003e nanobelt and tunable three-step electron transfer for enhanced photocatalytic property. Acs Appl Mater Interfaces 6(13):10044-10059. https://doi.org/10.1021/am502379q\u003c/li\u003e\n \u003cli\u003eZhang ZY, Hu YZ, Fu Z, Li ZH, Chen JD, Yuan M, Wu SX, Hong RD, Lin DQ, Chen XP, Cai JF, Wu ZY, Zhang YN, Fu DY, Shen ZW, Wang ZJ, Zhang F, Zhang R (2025) Localized\u0026ensp;Surface Plasmon Resonance-Enhanced SiC UV Photodetectors Based on Ordered Al/Al\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e Core-Shell Nanoparticle Arrays. Small (Weinheim an der Bergstrasse, Germany) 2025:2502011. https://doi.org/10.1002/smll.202502011\u003c/li\u003e\n \u003cli\u003eLi J, Xie GZ, Jiang J, Liu YY, Chen CX, Li WX, Huang JL, Luo XL, Xu M, Zhang QP, Yang M, Su YJ.(2023) Enhancing photodegradation of Methyl Orange by\u0026ensp;coupling\u0026ensp;piezo-phototronic\u0026ensp;effect\u0026ensp;and localized\u0026ensp;surface plasmon resonance. Nano energy 108:108234. https://doi.org/10.1016/j.nanoen.2023.108234\u003c/li\u003e\n \u003cli\u003eManiah K, Al-Otibi OF, Mohamed S, Said BA, AbdelGawwad RM, Yassin TM (2024) Synergistic\u0026ensp;antibacterial\u0026ensp;activity of biogenic\u0026ensp;AgNPs\u0026ensp;with antibiotics against multidrug resistant bacterial strains[J]. Journal of King Saud University. Science 36 (10):103461. https://doi.org/10.1016/j.jksus.2024.103461\u003c/li\u003e\n \u003cli\u003eZhang FZ, Zeng Y, Zheng MY, Zheng H, Fang M, Xie BX, Lin RG (2024) Photocatalytic activity and synergistic\u0026ensp;antibacterial effects\u0026ensp;of PCN-222@AgNPs\u0026ensp;under visible light irradiation. Journal of coordination chemistry 77(1-2):188-202. https://doi.org/10.1080/00958972.2024.2303734\u003c/li\u003e\n \u003cli\u003eWang P, Lu YG, Wang XF, Yu HG(2017) Co-modification of amorphous-Ti (IV) hole cocatalyst and Ni(OH)\u003csub\u003e2\u003c/sub\u003e electron cocatalyst for enhanced photocatalytic H\u003csub\u003e2\u003c/sub\u003e-production performance of TiO\u003csub\u003e2\u003c/sub\u003e. \u003cem\u003eAppl Surf Sci\u0026nbsp;\u003c/em\u003e391:259-266. https://doi.org/10.1016/j.apsusc.2016.06.108\u003c/li\u003e\n \u003cli\u003eKong LG, Dong YM, Jiang PP, Wang GL, Zhang HZ, Zhao N (2016) Light-assisted rapid preparation of a Ni/g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e magnetic composite for robust photocatalytic H\u003csub\u003e2\u003c/sub\u003e evolution from water. \u003cem\u003eJ Mater Chem A\u003c/em\u003e 4(25):9998-10007. https://doi.org/10.1039/c6ta03178a\u003c/li\u003e\n \u003cli\u003eBai L, Zhang XL, Ding ZJ, Wang XC, Huang YJ, Kannan P (2019) One-pot synthesis of Ag nanoparticles/ZnO nanorods heterostructures for organic dyes decoloring. J Taiwan Inst Chem E 103:118-125. https://doi.org/10.1016/j.jtice.2019.08.002\u003c/li\u003e\n \u003cli\u003eZhang WF, Zhang Y, Yu L, Wu NL, Huang HT, Wei MD (2019) TiO\u003csub\u003e2\u003c/sub\u003e-B nanowires via topological conversion with enhanced lithium-ion intercalation properties.\u003cem\u003eJ Mater Chem A\u003c/em\u003e 7 (8):3842-3847. https://doi.org/10.1039/c8ta10709b\u003c/li\u003e\n \u003cli\u003eOpra DP, Gnedenkov SV,Sinebryukhov SL(2019)Recent efforts in design of TiO\u003csub\u003e2\u003c/sub\u003e(B) anodes for high-rate lithium-ion batteries: A review. J. Power Sources 442: 227225. https://doi.org/10.1016/j.jpowsour.2019.227225\u003c/li\u003e\n \u003cli\u003eBai Y, Li E, Liu C, Yang ZH, Feng X, Lu XH, Chan KY (2009) Stability of Pt Nanoparticles and Enhanced Photocatalytic Performance in Mesoporous Pt (Anatase/TiO\u003csub\u003e2\u003c/sub\u003e(B)) Nanoarchitecture. J Mater Chem 19(38):7055-7061. https://doi.org/10.1039/b910240j\u003c/li\u003e\n \u003cli\u003eEddy DR, Permana MD, Sakti LK, Sheha GAN, Solihudin, Hidayat S, Takei A, Kumada N, Rahayu I (2023) Heterophase Polymorph of TiO\u003csub\u003e2\u0026nbsp;\u003c/sub\u003e(Anatase, Rutile, Brookite, TiO\u003csub\u003e2\u003c/sub\u003e(B)) for Efficient Photocatalyst: Fabrication and Activity. Nanomaterials 13(4):704. https://doi.org/10.3390/nano13040704\u003c/li\u003e\n\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"journal-of-sol-gel-science-and-technology","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"jsst","sideBox":"Learn more about [Journal of Sol-Gel Science and Technology](https://www.springer.com/journal/10971)","snPcode":"10971","submissionUrl":"https://submission.springernature.com/new-submission/10971/3","title":"Journal of Sol-Gel Science and Technology","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"silver nanoparticles, TiO2(B)/anatase heterojunctions, surface plasmon resonance, contact antibacterial, photocatalytic mechanism","lastPublishedDoi":"10.21203/rs.3.rs-7513011/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-7513011/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eThe TiO\u003csub\u003e2\u003c/sub\u003e microrods (TiO\u003csub\u003e2\u003c/sub\u003e MRs) with TiO\u003csub\u003e2\u003c/sub\u003e(B)/anatase biphase heterojunctions were synthesized through \u003ca href=\"https://www.baidu.com/s?rsv_idx=1\u0026amp;wd=hydrolyzing%E7%BF%BB%E8%AF%91\u0026amp;fenlei=256\u0026amp;usm=2\u0026amp;ie=utf-8\u0026amp;rsv_pq=efabfe7800007a47\u0026amp;oq=hydrolyze%E7%BF%BB%E8%AF%91\u0026amp;rsv_t=2a35nGL6cQ347lVFBdtgrTkjYzKrIkAT7glXlOKxNFqGxyO1oIYx8iOuFlE\u0026amp;sa=re_fy_huisou\" target=\"https://www.baidu.com/_blank\"\u003ehydrolyzing\u003c/a\u003e of precursor K\u003csub\u003e2\u003c/sub\u003eTi\u003csub\u003e4\u003c/sub\u003eO\u003csub\u003e9 \u003c/sub\u003eand calcining of hydrated H\u003csub\u003e2\u003c/sub\u003eTi\u003csub\u003e4\u003c/sub\u003eO\u003csub\u003e9\u003c/sub\u003e. An optimized amount of silver nanoparticles (AgNPs) loaded on TiO\u003csub\u003e2\u003c/sub\u003e MRs (Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs) was obtained via solvent evaporation followed by \u003cstrong\u003ethermal reduction\u003c/strong\u003e. The photocatalytic degradation rates reached 81.34% for MB over TiO\u003csub\u003e2\u003c/sub\u003e MRs, and 99.81% for RhB over Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs within 30 minutes under ultraviolet (UV) radiation, which demonstrated that TiO\u003csub\u003e2\u003c/sub\u003e(B)/anatase heterojunctions and Ag-TiO\u003csub\u003e2\u003c/sub\u003e Schottky Barrier markedly enhanced the photocatalytic activity owing to effective separation of photogenerated\u0026nbsp; carriers. Additionally, the scavenger experiments revealed that photoexcited holes (h\u003csup\u003e+\u003c/sup\u003e), superoxide (O\u003csub\u003e2\u003c/sub\u003e•\u003csup\u003e−\u003c/sup\u003e) and hydroxyl (HO•) radicals were actively involved in the photodegradation of RhB. Furthermore, the slightly improved RhB catalytic degradation rates for Ag/TiO\u003csub\u003e2\u003c/sub\u003e MRs under xenon lamp demonstrated the surface plasmon resonance effect generated from AgNPs. Besides, the well-dispersed AgNPs could act as a\u0026nbsp;\u003cstrong\u003econtrolled-release silver ion reservoir\u003c/strong\u003e, providing sustained antibacterial activity in the dark.\u003c/p\u003e","manuscriptTitle":"Low silver loaded biphase of TiO2 microrods with TiO2(B)/anatase and their photocatalytic and antibacterial properties","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-09-11 13:48:00","doi":"10.21203/rs.3.rs-7513011/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Revision requested","date":"2025-09-27T16:43:52+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-09-26T14:46:23+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-09-14T06:20:41+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"210049277976643890958116127380555698571","date":"2025-09-06T08:37:07+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"45187334911057576111222386785872062478","date":"2025-09-04T23:41:13+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2025-09-04T14:43:21+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2025-09-03T06:04:13+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2025-09-03T06:01:28+00:00","index":"","fulltext":""},{"type":"submitted","content":"Journal of Sol-Gel Science and Technology","date":"2025-09-02T03:46:33+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"journal-of-sol-gel-science-and-technology","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"jsst","sideBox":"Learn more about [Journal of Sol-Gel Science and Technology](https://www.springer.com/journal/10971)","snPcode":"10971","submissionUrl":"https://submission.springernature.com/new-submission/10971/3","title":"Journal of Sol-Gel Science and Technology","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"5d6ade60-d420-4984-9095-d3ca21e2f99c","owner":[],"postedDate":"September 11th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"under-review","subjectAreas":[],"tags":[],"updatedAt":"2026-01-06T15:53:52+00:00","versionOfRecord":[],"versionCreatedAt":"2025-09-11 13:48:00","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-7513011","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-7513011","identity":"rs-7513011","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}