Electrochemically synthesized Tin micro-nanometer powders for visible light photocatalytic degradation of Rhodamine B dye from polluted water

Electrochemically synthesized Tin micro-nanometer powders for visible light photocatalytic degradation of Rhodamine B dye from polluted water | 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 Electrochemically synthesized Tin micro-nanometer powders for visible light photocatalytic degradation of Rhodamine B dye from polluted water Yukun Lu, Yaojie Zhang, Jiale Zhang, Zhaoyang Li, Feiyang Hu, and 5 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-4270111/v1 This work is licensed under a CC BY 4.0 License Status: Under Review Version 1 posted 11 You are reading this latest preprint version Abstract Tin (Sn) micro-nanoparticles with special pine tree dendritic morphology were synthesized by using tin foil as the anode and titanium as the cathode through simple anodization method. Surprisingly, it is found that the morphology of Sn particles is closely related to factors such as the type of electrolyte, the concentration of the electrolyte, and the different applied voltages, and briefly discussed the influence of various factors on the growth of Sn particles. In addition, Sn particles are calcined under different temperature conditions to obtain Sn/SnO 2 hybrid materials with different tin dioxide (SnO 2 ) contents. The changes in morphology and the phase of SnO 2 crystal lattices were characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD), respectively, which proved the successful synthesis of Sn/SnO 2 mixed materials. Finally, the Sn/SnO 2 hybrid material with metal-doped modified semiconductor properties was used to photocatalytic degradation of simulated organic pollutants rhodamine B (RhB). It was found that the photocatalytic degradation efficiency of the Sn/SnO 2 hybrid material under simulated sunlight conditions is near 90% in 5 h. Therefore, this work provides a convenient and effective environmental protection approach for the treatment of architecture and industrial dyes. Tin micro-nanoparticles morphology Sn/SnO2 hybrid materials Photocatalytic activity Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 1 Introduction Tin (Sn) particles play an important role as electronic interconnect materials in electronic devices [ 1 , 2 ]. As the demand for interconnection of components and fine-pitch printing is continuously increasing, Sn nanoparticles are considered as the most promising candidate for conductive inkjet printing material to replace traditional nano-silver [ 3 , 4 ]. Sn nanoparticles have been received wide attention as one of the promising anode materials for lithium batteries, the results show that the theoretical value of its capacitance can be as high as 993 mA·h·g − 1 , which is about three times that of carbon anode materials [ 5 , 6 ]. Recently, in order to improve the performance of lithium-ion batteries performance, Sn and carbon nanocomposites have been reported with high capacity and capacity retention when used as anode materials [ 7 , 8 ]. In addition, Sn nanoparticles exhibit excellent wear resistance, and compared to the size of particles formed in glasses with no or little Sn, it can accelerate the formation of gold clusters in silicate glasses and induce a reduction in the average size of gold nanoparticles [ 9 ]. Based on the above knowledge, Sn nanomaterials have huge application prospects in many areas of human life, so the research on the preparation of nano-Sn is getting more and more attention from researchers. Various procedures have been proposed and applied to obtain Sn nanoparticles, such as mechanical alloying technology [ 10 ], arc discharge technology [ 11 ], metal vapor condensation technology [ 12 ], liquid-phase reduction [ 13 ], physical vapor deposition (PVD) [ 14 ], chemical liquid deposition (CLD) [ 15 ], electrochemical method [ 16 ], reverse micelle method [ 17 ] and so on. For example, Chee et al . [ 18 ] used stannous octoate as a raw material, sodium borohydride as a reducing agent, and polyvinylpyrrolidone (PVP) as a surfactant to study the effects of reaction temperature, drying temperature, ultrasonic vibration, and centrifugal speed on the size of Sn nanoparticles. It was found that the size of Sn nanoparticles increased with the increase of reaction temperature and drying temperature, and the agglomeration of Sn nanoparticles was aggravated with the increase of ultrasonic and centrifugal speed [ 19 ]. However, in these methods, the Sn nanoparticles obtained by some methods are prone to agglomeration, results in uneven size and contains many impurities (such as mechanical alloying technology and arc discharge technology), some require reaction in a vacuum environment (such as PVD method), and some require harsh experimental conditions and complex operations (such as metal vapor condensation technology) [ 20 – 22 ]. Only the electrochemical method based on electrolysis theory is simple in operation and low in cost, and it is easy to obtain Sn nanoparticles with controllable and uniform morphology by controlling the reaction conditions [ 23 , 24 ]. In addition, semiconductor oxides play a huge role in the field of catalytic degradation due to their unique electron and hole characteristics [ 25 ]. Tin dioxide (SnO 2 ) as an n-type wide bandgap semiconductor material, which is widely used in the cleaning and purification of organic pollutants in water and air due to its unique photocatalytic activity and good chemical stability [ 26 , 27 ]. Furthermore, as a photocatalyst, SnO 2 has mild reaction conditions, fast reaction speed, high catalytic activity, strong oxidation ability, low energy consumption, and no secondary pollution, so it is considered to be one of the most promising green catalysts [ 28 – 30 ]. Elango et al. [ 31 ] synthesized SnO 2 nanoparticles by green method using Persia Americana seed methanolic extract, it was found that the synthesized SnO 2 nanoparticles had a size of 4 nm and exhibited an excellent photocatalytic degradation effect on the organic dye phenolsulfonphthalein (phenol red). In this paper, Sn particles with a dendritic microstructure were generated at the cathode by a simple electrochemical anodic oxidation method, and then metal Sn-doped semiconductor SnO 2 hybrids with certain photocatalytic activity were obtained by further high-temperature oxidation treatment. With the help of SEM and XRD measurements, the morphologies and structures of the Sn and Sn/SnO 2 microparticles were characterized respectively. Specifically, the influencing parameters such as applied potential, electrolyte and its concentration were discussed, and the growth of process of Sn microparticles with dendritic structure was also discussed. Different ratio of Sn and SnO 2 in the final product was get after different heat treatment temperature. The final photocatalytic degradation experiment results found that the photocatalytic activity Sn/SnO 2 particles was superior to that of the pure Sn particles estimated with the degradation of rhodamine B (RhB) under simulated solar light. 2 Experimental procedures 2.1 Materials High-purity tin flake (1000 × 1000 × 1 mm, 99.99%) and high-purity titanium flake (1000 × 1000 × 1 mm, 99.99%) were obtained from Beijing Jinyuan New Material Technology Co., Ltd. (Beijing, China). Ethanol (CH 3 CH 2 OH, 99.7%), acetone (CH 3 COCH 3 , AR), isopropanol (C 3 H 8 O, AR) and methanol (CH 3 OH, AR) were purchased from Shanghai Aladdin Reagent Co., Ltd., China. Hydrofluoric acid (HF, AR, 40%), nitric acid (HNO 3 , AR), Ethylenediamine (C 2 H 8 N 2 , AR) and ammonium fluoride (NH 4 F, AR, 98%) were provided by Shanghai McLean Biochemical Technology Co., Ltd., China. Rhodamine B (RhB) was supplied by Tianjin Bodi Chemical Reagent Co. Ltd. (AR, Tianjin, China). Distilled water was used throughout the experiments. All reagents were of analytical grade and used without further purification. 2.2 Preparation of Sn particles and Sn/SnO 2 hybrid Before anodization, it needs to clean and polish the Sn and Ti sheets. Specifically, the Sn sheets and Ti sheets cut into 2 cm × 2 cm were sonicated in acetone, isopropanol and methanol for 10 min in turn. Then, the Sn sheet was physically polished with sandpaper, and the Ti sheet was chemically polished in a mixture of V(HF):V(HNO 3 ):V(H 2 O) = 1:4:5, and last cleaned with deionized water. Sn particles are obtained through a unique electrochemical method, the experiments were performed at the room temperature in a two-electrodes using Sn plate as the anode and Ti plate as the cathode. The electrolyte used was ethylene glycol solutions of NH 4 F which concentration was in the range from 0.04 M to 0.2 M. A constant voltage was applied for each experiment, ranging from 5 to 50 V. After electrochemical reaction for a period of time, the coating deposited on the cathode Ti sheet was collected. The products (Sn particles) were washed and centrifuged several times with distilled water and absolute ethanol respectively to remove the impurities, and then dried in a drying oven at 70°C. The Sn particles are subjected to different high-temperature (450 ℃, 550 ℃, and 600 ℃) oxidation treatments to obtain the corresponding Sn/SnO 2 hybrid. 2.3 Characterization The phases and structures of the prepared samples were measured with a Rigaku D/Max2500PC X-ray diffraction (XRD) equipped with graphite monochromatized Cu Kα radiation (λ = 0.15418 nm), using a scanning rate of 4°·min − 1 in 2θ rage from 10° to 80°. The morphology of the products was characterized by a scanning electron microscope (SEM, SU-70) with acceleration voltage of 15 KV. The concentration of RhB in the solution was then measured by using a UV–Vis spectrophotometer (UV9000) at a wavelength of 554 nm. 2.4 Photocatalytic activity performance tests and electrochemical performance analysis The photocatalytic activity of the product was evaluated through the photodegradation of Rhodamine B (RhB) under a simulated solar light irradiation. The experimental process could be summarized as follows: 0.05 g of the as-prepared samples were dispersed ultrasonically for 2 min in 50 mL of RhB solution with a concentration of 10 mg·L –1 . A 300 W xenon lamp without any optical filters was employed to simulate the solar light irradiation. The electrochemical performance (transient photocurrent density) of Sn/SnO 2 hybrid was detected by the three-electrode system of the electrochemical workstation (Autolab, Metrohm Co. Ltd.). Under the intermittent irradiation of Xenon lamp to simulate sunlight, a nickel foam (4 cm 2 ) coated with 20 mg catalyst was used as working electrode, platinum electrode as counter electrode, saturated calomel electrode as reference electrode, and electrolyte selected as 0.1 mol/L Na 2 SO 4 solution. 3 Results and discussion 3.1 Morphological characterization of Sn particles obtained under different conditions Tin (Sn) particles generated at the cathode by electrochemical methods, the morphology and size of Sn microparticles can be controlled by adjusting the experimental conditions, such as composition of electrolyte (fluoride ion content, deionized water content), applied voltage, and reaction time [ 32 – 34 ]. In order to establish the impact of fluoride ion concentration on the micro-nano structure, we prepared samples by changing the NH 4 F content (0.04 mol/L, 0.08 mol/L, 0.15 mol/L, 0.20 mol/L, respectively) based on the consistency of other factors (deionized water content of 5 vol%, reaction voltage of 15 V and reaction time of 5 h). As shown in Fig. 1 , Sn particles present a unique dendritic morphology, and the shape of the dendrites is closely related to the concentration of NH 4 F. From the SEM of Fig. 1 a, it can be seen that at low NH 4 F content (0.04 mol/L), the obtained dendritic Sn particles are larger in size, the stems are slightly bent, and the whole morphology is rough and irregular. When the concentration of NH 4 F increased to 0.08 mol/L, the morphology of dendritic products tended to be regular, the stems tended to be straight and the length of branches decreased (Fig. 1 b). When the NH 4 F concentration is further increased to 0.15 mol/L, the branches of dendritic Sn particles become finer and the stem length is decreases to 50 µm (Fig. 1 c). When the NH 4 F content reaches 0.20 mol/L, large-grained dendrites appear, and the dendritic morphology becomes irregular and agglomerated (Fig. 1 d). It can be concluded that the content of NH 4 F has a great influence on the morphology of tin micro-nano powder, and when its concentration is 0.15 mol/L, the perfect product of Sn dendrite can be obtained. Next, we analyzed the effect of the content of a small amount of deionized water in the electrolyte solution on the morphology of Sn micro-nanostructures. As shown in Fig. 2 a and 2 b, on the basis of other conditions being uniform (NH 4 F content of 0.15 mol/L, reaction voltage of 15 V and reaction time of 5 h), at low deionized water content (1.5 and 3 vol%), the dendritic Sn particles are irregular in shape and accompanied by many debris. When the deionized water content increased to 5 vol%, the crystal morphology of the obtained dendritic products tends to be regular and perfect, and the fine branches become numerous and dense (Fig. 2 c). When the deionized water content is further increased to 10 vol%, the stem length of dendritic Sn particles increases, but the fine branches tend to be sparse (Fig. 2 d). For the electrochemical reaction process, the applied voltage also has a great influence on the morphology of the deposited product on the electrode [ 35 , 36 ]. Figure 3 is the SEM of Sn microparticles obtained under different reaction voltages, from Fig. 3 a, after 5 h electrochemical reaction, the products obtained by applying a voltage of 5 V are mostly granular, and the dendritic morphology is not perfect. When the applied voltage increased to 10 V, the morphology of dendritic products gradually formed, but the thin branches are not completely bifurcation (Fig. 3 b). As the voltage continues to increase to 15 V and 30 V, it can be seen from Fig. 3 c and d that the morphology of dendritic Sn particles tends to be regular, and there is no obvious change in the SEM of 15 V and 30 V. The growth process of Sn microparticles with dendritic structure was studied by controlling the reaction time. In order to explore the crystal growth of Sn particles, the growth process of the crystal product is studied from the nanometer size in a short time (5 min, 30 min, 60 min and 90 min). Under the condition of an applied voltage of 15 V, after the electrochemical reaction for 5 min, the Sn nanoparticles deposited on the cathode show a nano-dispersion state, and the Sn particle size is about 25 nm (Fig. 4 a). When the reaction time reaches 30 min, the Sn nanoparticles grow to about 100 nm, but remain independent from each other (Fig .4b). From Fig. 4 c, as the reaction time is above 60 min, Sn nanoparticles grow further and some begin to connect and merge with each other. With the time increased to 90 min, for Sn nanoparticles with increasing size, the compatibility phenomenon is more obvious and the dendritic rudiment appears (Fig. 4 d). Until the reaction time increases to 5 h, the Sn particles show a perfect dendritic morphology. 3.2 Mechanism of electrochemical method to generate Sn particles Combining the growth morphology of Sn crystal products under different conditions above, and based on the theoretical basis for the preparation of metal particles by the electrochemical anodic oxidation-cathode precipitation method, we get that the formation mechanism of Sn particles is mainly divided into four stages. In the first stage, due to the hydrolysis of NH 4 F, the electrolyte is weakly acidic, during the electrolysis process [ 37 ], the Sn sheet as anode is oxidized, and many micro bubbles appear on the cathode Ti sheet. The main reactions of the two electrodes are as follows: Anode: Sn → Sn 2+ + 2e − (1) Cathode: 2H + + 2e − → H 2 (2) In the second stage, the fluoride ion (F − ) in the electrolyte solution is complexed with the tin ion (Sn 2+ ) generated by the anode to obtain SnF 4 2− , and the specific reaction is: Sn 2+ + 4F − → SnF 4 2− (3) In the third stage, the SnF 4 2− reach the vicinity of the cathode under the action of magnetic stirring and are reduced to metal Sn particles by obtaining electrons, the reaction is as follows: SnF 4 2− + 2e − → Sn + 4F − (4) In the fourth stage, when the metal Sn crystal nucleus starts to precipitate on the cathode, as the reaction proceeds, the Sn particles gradually grow and become larger in size, and with the different reaction conditions, the morphology of the obtained Sn particles is also different. 3.3 Characterization analysis of Sn/SnO 2 after Sn particles treated at different high temperatures By exploring the influence of different conditions on the crystal morphology, the optimal conditions for the electrochemical method to prepare Sn particles are obtained: in the ethylene glycol electrolyte solution containing NH 4 F, the content of NH 4 F is 0.15 mol/L, the deionized water content was 5 vol%, and the reaction is carried out for 5 h under the applied working voltage of 15 V. In order to make the product have higher photocatalytic activity, the Sn particles with dendritic crystal morphology were then subjected to high-temperature calcination treatment at 450°C, 550°C and 600°C, respectively [ 38 , 39 ], and the SEM of the obtained samples are shown in Fig. 5 a-c. Compared with the Sn particles, the morphology of the samples changed after high temperature treatment. It can be seen from Fig. 5 a that when the temperature is set at 450°C, the surface of the sample is scattered due to oxidation, but the overall dendritic skeleton morphology remains unchanged. When the heat treatment temperature increased to 550°C, the branches of dendritic Sn particles gathered together and a large number of micropores appeared on the surface with the intensification of the oxidation degree (Fig. 5 b). When the temperature reaches 600°C, it can be seen from Fig. 5 c that the dendritic morphology of the sample becomes less obvious, and the surface tends to be loose and porous. In summary, it can be concluded that the morphology of the Sn particles obtained by the electrochemical method changes from a regular dendritic structure to a loose and porous structure after different high-temperature treatments, which provides abundant catalytic active sites for the obtained samples as photocatalysts [ 40 , 41 ]. To analyze the crystal structure and phase composition of the as-prepared samples after high-temperature treatment, XRD was carried out. The XRD patterns of the as-prepared products are shown in Fig. 5 d. For the obtained Sn particles, all the diffraction peaks are in well agreement with the literature values of the tetragonal phase of metallic Sn (JCPDS No.04-0673) [ 42 – 44 ]. Nearly no other peaks of impurities are detected, showing that the obtained Sn particles are of high purity. After Sn microparticles are treated at different high temperatures (450 ℃, 550 ℃ and 600 ℃), the peaks of cassiterite SnO 2 (JCPDS file No. 41-1445) can be also found in the patters [ 45 – 47 ]. Therefore, the main component of the sample obtained after high temperature treatment is the hybrid compound composed of Sn and n-type semiconductor SnO 2 (Sn/SnO 2 ). It is worth noting that with the increase of heat treatment temperature, the diffraction peak of metal Sn in the hybrid gradually weakens, and the characteristic peak of SnO 2 gradually increases, indicating that the oxidation degree of Sn particles deepens with the increase of temperature. 3.4 Photocatalytic performance of Sn/SnO 2 n-type semiconductor SnO 2 has excellent stability and photocatalytic activity [ 48 – 50 ]. In this work, the Sn/SnO 2 hybrid with metal Sn-doped semiconductor SnO 2 properties obtained by high-temperature treatment of dendritic Sn particles can further improve the photocatalytic performance of traditional catalyst SnO 2 [ 51 , 52 ]. To eliminate the effect of adsorption on photocatalysis, for each experiment, 50 mg of catalyst powder was added to 50 mL of RhB solution and stirred for 1 h in the dark to obtain adsorption/desorption equilibrium [ 53 ]. During light irradiation, the catalyst was kept in suspension by a magnetic stirrer, and 2 ml of the reaction solution was aspirated with a pipette every 30 min and centrifuged immediately to separate the catalyst from the solution. Finally, the concentration of RhB in the solution after a fixed time was measured at a wavelength of 554 nm by a UV-visible spectrophotometer [ 54 ]. The specific degradation efficiency calculation formula is as follows [ 55 ]: The degradation efficiency = [( C 0 - C t )/ C 0 ] × 100% (5) where C 0 is the initial concentration of RhB, C t is the concentration of RhB at time t . From Fig. 6 a, after illumination for 5 h, compared with commercial SnO 2 , the photocatalytic efficiency of the Sn/SnO 2 hybrid obtained in this work has been greatly improved, especially for the degradation efficiency of the catalyst obtained by calcination at 550°C as high as 89.8%. It is worth noting that when the calcination temperature continues to increase to 600°C, the photocatalytic efficiency of the hybrids decreases, which may be related to the electron mismatch in the Sn and SnO 2 heterojunction. In order to verify the accuracy of the above photocatalytic efficiency and predict that the degradation of RhB by the catalyst may be related to the rapid interfacial transfer of photogenerated charge carriers and the subsequent effective charge separation, the photocurrent response behavior of the sample electrode in 0.1M Na 2 SO 4 electrolyte under intermittent visible light irradiation was tested using a three-electrode system in an electrochemical workstation [ 56 , 57 ]. As shown in Fig. 6 b, the prepared electrodes of different samples have a very obvious change in the response current under the condition of intermittent switching of the xenon lamp for 15 s. The Sn/SnO 2 (550°C) electrode demonstrated a stronger transient photocurrent response (0.38 mA/cm 2 ) under visible light illumination, which was higher than that of commercial SnO 2 (0.26 mA/cm 2 ), Sn/SnO 2 (450°C) (0.33 mA/cm 2 ), and Sn/SnO 2 (600°C) (0.36 mA/cm 2 ). In addition, after three cycles of light cycles, the current density under light conditions is basically constant, which proves that the prepared catalyst has good stability. In order to more directly reflect the photocatalytic performance of the catalyst on RhB in different time periods, the time-dependent UV-Vis absorption spectrum of RhB with Sn/SnO 2 (550°C) electrode is also operated and shown in Fig. 6 c. It can be clearly seen from the figure that with the passage of degradation time, the UV-Vis absorption peak intensity of RhB in the solution decreased significantly at 554 nm. The recycling performance of photocatalysts is considered to be a key factor for evaluating the green sustainable catalysts, the cyclic experiments of Sn/SnO 2 (550°C) are conducted for seven runs and the result is depicted in Fig. 6 d. After the first measurement, the catalyst is centrifuged, washed three times with deionized water and ethanol, and dried for the next cycle experiment. From the experimental results, it can be found that the degradation efficiency of the catalyst Sn/SnO 2 (550°C) to RhB can still achieve more than 80.0% after 5 cycles, and the degradation efficiency decreases but still remains above 70.0% after 7 cycles. The degradation of performance may be related to the surface deactivation caused by the adsorption of RhB degradation products to the surface of the catalyst. Therefore, these results indicate that the photocatalyst obtained in this study has good reusability. 3.5 Photocatalytic mechanism of Sn/SnO 2 The above results indicate that the Sn doped SnO 2 samples have shown much improved photocatalytic activity on the photodegradation of RhB than the pure commercial SnO 2 . The UV-vis diffuse reflectance spectra of the pure SnO 2 and calcined sample Sn/SnO 2 are showed in Fig. 7 a, it can be clearly seen that Sn/SnO 2 have good light absorption than pure SnO 2 in the visible light absorption range with a range of 400–750 nm, which indicates that doped Sn enhanced significantly visible light absorption of SnO 2 catalyst. The direct band gap ( E g ) values of different catalysts are estimated from the ( Ahν ) 2 versus photon energy ( hν ) plot as showed in the Fig. 7 b [ 58 ]. As depicted in Fig. 7 b, the band gap of Sn/SnO 2 have been narrowed from 3.85 eV (pure SnO 2 ) to 3.82 (calcined at 450°C), 3.76 (calcined at 550°C) and 3.80eV (calcined at 600°C), respectively. It is worth mentioning that the band gap of samples obtained at 550°C is the lowest and the photocatalytic effect is the best. The surface is attributed to the unique morphology to provide abundant active sites. The deep theory is that the appropriate amount of Sn-doped SnO 2 catalyst obtained at 550°C promotes the transfer of photogenerated charge and extends the lifespan of photogenerated charge. The probable photocatalytic mechanism of Sn-doped SnO 2 hierarchical structures for degradation of RhB and schematic electronic structure for significantly improving photocatalytic performance are illustrated in Fig. 7 c. Under visible light excitation, electrons in the valence band (VB) of Sn-doped SnO 2 catalyst can be excited to the conduction band (CB) of the catalyst, while forming the same number of holes in VB (Eqs. (6)), leading to the formation of photogenerated electron–hole pairs [ 59 , 60 ]. Compared to pure SnO 2 , the Sn-doped SnO 2 hierarchical structure shows the stronger light absorption and lower band gap and the, therefore, more charge carriers can be excited in the process and then participate in following photocatalytic reactions [ 61 , 62 ]. The reactive electrons (e − ) from the Sn/SnO 2 reduce O 2 to·O 2 • − (Eqs. (7)) [ 63 ]. Meanwhile, the reactive holes (h + ) oxidize RhB to its radical cation either directly (Eqs. (10)) or through a primarily formed • OH produced by the oxidation of ubiquitous water (Eqs. (8)) [ 64 , 65 ]. O 2 • − and • OH are proven to be the main active species, which can eventually convert organic dyes (RhB) into CO 2 , H 2 O and others (Eqs. (9) and (11)) [ 66 ]. Sn/SnO 2 + visible light →Sn/SnO 2 + e − (CB) + h + (CB) (6) e − + O 2 → O 2 • − (7) h + + H 2 O → • OH + H + (8) RhB + O 2 • − → CO 2 + H 2 O + Other products (9) RhB + h + → CO 2 + H 2 O + Other products RhB + • OH → CO 2 + H 2 O + Other products (10) (11) 4 Conclusions Sn microparticles with dendritic structure were successfully synthesized from the cathode via a simple electrochemical method. It was found through SEM that the morphology and size of Sn particles were related to the experimental parameters, including composition of electrolyte (fluoride ion content, deionized water content), applied voltage, and reaction time. As a result, the optimal conditions for the electrochemical method to prepare dendritic Sn particles: in the ethylene glycol electrolyte solution containing NH 4 F, the content of NH 4 F is 0.15 mol/L, the deionized water content was 5 vol%, and the reaction is carried out for 5 h under the applied working voltage of 15 V. Then dendritic Sn particles were subjected to high-temperature calcination to obtain products that not only had numerous microporous morphology, but also contained hybrid phases of Sn and SnO 2 . The abundant catalytic active sites on the surface of the product and the characteristics of Sn-doped P-type semiconductor SnO 2 make it an excellent photocatalyst. Especially when the calcination temperature is 550°C, the Sn/SnO 2 product shows superior photocatalytic activity to other samples toward the degradation of RhB. In conclusion, this work provides a new strategy for the effective degradation of architecture and industrial dyes by a simple electrochemical method. Declarations Declaration of competing interest The authors declare that they have no competing financial interests or personal relationships that could have influenced the work reported in this paper. Acknowledgements The authors extend their appreciation to Taif University, Saudi Arabia for supporting this work through project number (TU-DSPP-2024-01). Author contribution Yukun Lu prepared the materials and conducted most of the measurements and data analysis. Yaojie Zhang and Jiale Zhang contributed to the data analysis. Zhaoyang Li, Feiyang Hu and Duo Pan conceived the idea, wrote the paper, and coordinated the overall project. Saad Melhi and Xuetao Shi revised the paper. Mohammed A. Amin provided supervision and resources. Zeinhom M. El-Bahy reviewed and revised the manuscript. All authors reviewed the manuscript. Funding None. Data availability The authors confirm that the data supporting the findings of this study are available within the article. Raw data that support the findings of this study are available from the corresponding author, upon reasonable request. References Zou C-D, Gao Y-L, Bin Y, Zhai Q-J (2010) Size-dependent melting properties of Sn nanoparticles by chemical reduction synthesis. T Nonferr Metal Soc 20:248–253. https://doi.org/10.1016/S1003-6326(09)60130-8 Liang S, Cheng YJ, Zhu J, Xia Y, Müller-Buschbaum P (2020) A chronicle review of nonsilicon (Sn, Sb, Ge)‐based lithium/sodium‐ion battery alloying anodes. 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Appl Catal B: Environ 210:88–96. https://doi.org/10.1016/j.apcatb.2017.03.059 Xie K, Wei S, Alhadhrami A, Liu J, Zhang P, Elnaggar AY, Zhang F, Mahmoud MHH, Murugadoss V, El-Bahy SM, Wang F, Li C, Li G (2022) Synthesis of CsPbBr 3 /CsPb 2 Br 5 @silica yolk-shell composite microspheres: precisely controllable structure and improved catalytic activity for dye degradation. Adv Compos Hybrid Mater 5:1423–1432. https://doi.org/10.1007/s42114-022-00520-4 Additional Declarations No competing interests reported. Supplementary Files floatimage1.png Graphical Abstract Tin (Sn) micro-nanoparticles with special pine tree dendritic morphology are synthesized through simple anodization method, and the final product Sn/SnO 2 particles after different heat treatments show superior photocatalytic degradation of RhB under simulated solar light. Cite Share Download PDF Status: Under Review Version 1 posted Editorial decision: Revision requested 05 May, 2024 Reviews received at journal 04 May, 2024 Reviewers agreed at journal 04 May, 2024 Reviews received at journal 03 May, 2024 Reviews received at journal 03 May, 2024 Reviewers agreed at journal 26 Apr, 2024 Reviewers agreed at journal 24 Apr, 2024 Reviewers invited by journal 24 Apr, 2024 Editor assigned by journal 24 Apr, 2024 Submission checks completed at journal 18 Apr, 2024 First submitted to journal 15 Apr, 2024 You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-4270111","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":292974993,"identity":"9fec6ba6-4539-4c9a-a88f-d078f52c7ae2","order_by":0,"name":"Yukun Lu","email":"","orcid":"","institution":"Shangqiu Normal University","correspondingAuthor":false,"prefix":"","firstName":"Yukun","middleName":"","lastName":"Lu","suffix":""},{"id":292974995,"identity":"52b7c248-0bd5-43b1-8942-b33a99ebbd5c","order_by":1,"name":"Yaojie Zhang","email":"","orcid":"","institution":"Ordos Institute of Technology","correspondingAuthor":false,"prefix":"","firstName":"Yaojie","middleName":"","lastName":"Zhang","suffix":""},{"id":292974998,"identity":"e75b0fab-f371-47c3-857d-0f58ace4f654","order_by":2,"name":"Jiale Zhang","email":"","orcid":"","institution":"Shangqiu Normal University","correspondingAuthor":false,"prefix":"","firstName":"Jiale","middleName":"","lastName":"Zhang","suffix":""},{"id":292974999,"identity":"0be63691-25b2-433c-85ff-825e7cc07e0a","order_by":3,"name":"Zhaoyang Li","email":"","orcid":"","institution":"Shangqiu Normal University","correspondingAuthor":false,"prefix":"","firstName":"Zhaoyang","middleName":"","lastName":"Li","suffix":""},{"id":292975000,"identity":"f4f3d06c-0aaf-405c-88a0-ff3d82d4ed2a","order_by":4,"name":"Feiyang Hu","email":"","orcid":"","institution":"Jiangxi Agricultural University","correspondingAuthor":false,"prefix":"","firstName":"Feiyang","middleName":"","lastName":"Hu","suffix":""},{"id":292975001,"identity":"d7d6464d-a725-49f1-a2d3-0fb973cb6718","order_by":5,"name":"Duo Pan","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA3klEQVRIiWNgGAWjYJACCQjFfABCHyBeC1sCyVp4DIjTYs5+9uBtnoo7cubtZz5//NnGIMd3I4HxcwEeLZY9ecnWPGeeGcucyd1gINnGYCx5I4FZegYeLQYHcsykedsOJ86Q4N2QYNjGkLjhRgIbMw8+LeffgLXUz5DgeXAgsY2hnrCWGxBbEiQkeBgbDrYxJBgQ0mI5442x5Zwzhw1n8KQZMzackzCceeZhszQ+Leb8OYY33lQclpdgP/z4448yG3m+48kHP+N1GBofFEeMDXg0YGoZBaNgFIyCUYAJAMRzSMXI0OhCAAAAAElFTkSuQmCC","orcid":"","institution":"Zhengzhou University, Ministry of Education, Zhengzhou University","correspondingAuthor":true,"prefix":"","firstName":"Duo","middleName":"","lastName":"Pan","suffix":""},{"id":292975002,"identity":"2c122a12-2ba4-437a-99fc-7cd63e0ff722","order_by":6,"name":"Saad Melhi","email":"","orcid":"","institution":"University of Bisha","correspondingAuthor":false,"prefix":"","firstName":"Saad","middleName":"","lastName":"Melhi","suffix":""},{"id":292975003,"identity":"fa260dcb-faee-4150-96f2-c252aea30a2f","order_by":7,"name":"Xuetao Shi","email":"","orcid":"","institution":"Northwestern Polytechnical University","correspondingAuthor":false,"prefix":"","firstName":"Xuetao","middleName":"","lastName":"Shi","suffix":""},{"id":292975004,"identity":"377799b7-9446-4cf7-81e5-6aa476bc60b6","order_by":8,"name":"Mohammed A. 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(\u003cstrong\u003ed\u003c/strong\u003e) 0.20 mol/L\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-4270111/v1/e36d7ab8039be3068b4a3464.png"},{"id":55515312,"identity":"9320ffe3-a956-4cf3-8c92-802ac7969e43","added_by":"auto","created_at":"2024-04-29 13:09:13","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":1371500,"visible":true,"origin":"","legend":"\u003cp\u003eSEM images of the Sn microparticles prepared with different deionized water content (\u003cstrong\u003ea\u003c/strong\u003e) 1.5 vol%, (\u003cstrong\u003eb\u003c/strong\u003e) 3 vol%, (\u003cstrong\u003ec\u003c/strong\u003e) 5 vol% and (\u003cstrong\u003ed\u003c/strong\u003e) 10 vol%\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-4270111/v1/8f78007186a09fbc4b0e067b.png"},{"id":55516582,"identity":"12a84072-6c9c-4e8b-b205-316e2846a771","added_by":"auto","created_at":"2024-04-29 13:17:13","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":781236,"visible":true,"origin":"","legend":"\u003cp\u003eSEM images of Sn microparticles prepared using different applied voltage (\u003cstrong\u003ea\u003c/strong\u003e) 5 V, (\u003cstrong\u003eb\u003c/strong\u003e) 10 V, (\u003cstrong\u003ec\u003c/strong\u003e) 15 V and (\u003cstrong\u003ed\u003c/strong\u003e) 30 V\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-4270111/v1/310d5facd92ed99d216e54e9.png"},{"id":55514226,"identity":"96e73f15-f6fd-4179-95dd-924014a6521c","added_by":"auto","created_at":"2024-04-29 13:01:13","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":780278,"visible":true,"origin":"","legend":"\u003cp\u003eSEM images of the Sn microparticles obtained at 15 V with different reaction time (\u003cstrong\u003ea\u003c/strong\u003e) 5 min, (\u003cstrong\u003eb\u003c/strong\u003e) 30 min, (\u003cstrong\u003ec\u003c/strong\u003e) 60 min and (\u003cstrong\u003ed\u003c/strong\u003e) 90 min\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-4270111/v1/6a24c265cf7c1964b7152a41.png"},{"id":55514229,"identity":"272e8cc6-0a01-4a08-9ed7-7b8d38abd0b8","added_by":"auto","created_at":"2024-04-29 13:01:13","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":705753,"visible":true,"origin":"","legend":"\u003cp\u003eSEM images of the Sn/SnO\u003csub\u003e2\u003c/sub\u003e microparticles obtained with different calcination temperature (\u003cstrong\u003ea\u003c/strong\u003e) 450 °C, (\u003cstrong\u003eb\u003c/strong\u003e) 550 °C and (\u003cstrong\u003ec\u003c/strong\u003e) 600 °C, (\u003cstrong\u003ed\u003c/strong\u003e) XRD patterns of Sn particles and Sn/SnO\u003csub\u003e2\u003c/sub\u003e products prepared with different calcination temperature\u003c/p\u003e","description":"","filename":"5.png","url":"https://assets-eu.researchsquare.com/files/rs-4270111/v1/21250e565c04cbd5c4804c42.png"},{"id":55514223,"identity":"12176a74-2cc7-480c-a3f7-ac9e9dadcf55","added_by":"auto","created_at":"2024-04-29 13:01:13","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":406564,"visible":true,"origin":"","legend":"\u003cp\u003e(\u003cstrong\u003ea\u003c/strong\u003e) Degradation efficiency of RhB with various catalysts, (\u003cstrong\u003eb\u003c/strong\u003e) The photocurrent density of various catalysts, (\u003cstrong\u003ec\u003c/strong\u003e) The absorption spectra of RhB with Sn/SnO\u003csub\u003e2\u003c/sub\u003e (550 °C) as photocatalyst in different reaction time, and (\u003cstrong\u003ed\u003c/strong\u003e) The cycles of photocatalytic experiment of Sn/SnO\u003csub\u003e2\u003c/sub\u003e (550 °C) for RhB degradation\u003c/p\u003e","description":"","filename":"6.png","url":"https://assets-eu.researchsquare.com/files/rs-4270111/v1/25802d118d5baf41e03b670c.png"},{"id":55514228,"identity":"8673d467-188f-4e77-804e-647913a5fe20","added_by":"auto","created_at":"2024-04-29 13:01:13","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":394895,"visible":true,"origin":"","legend":"\u003cp\u003e(\u003cstrong\u003ea\u003c/strong\u003e) UV-Vis spectra and (\u003cstrong\u003eb\u003c/strong\u003e) plots of (\u003cem\u003eAhν\u003c/em\u003e)\u003csup\u003e2\u003c/sup\u003e vs. \u003cem\u003ehν\u003c/em\u003e of different catalysts, (\u003cstrong\u003ec\u003c/strong\u003e) Photoresponse mechanism of the Sn-doped SnO\u003csub\u003e2\u003c/sub\u003e (550 °C)\u003c/p\u003e","description":"","filename":"7.png","url":"https://assets-eu.researchsquare.com/files/rs-4270111/v1/d5510367594a75446b7e3f87.png"},{"id":55517440,"identity":"64bf13d8-219a-4f2a-aa5d-2c1fbc689297","added_by":"auto","created_at":"2024-04-29 13:25:15","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":5172923,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-4270111/v1/2a99910b-8454-4b78-9f2a-bd5ba3dfea8b.pdf"},{"id":55514227,"identity":"ba696675-6d4e-4c75-ac51-30e07e2303e8","added_by":"auto","created_at":"2024-04-29 13:01:13","extension":"png","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":540685,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eGraphical Abstract\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eTin (Sn) micro-nanoparticles with special pine tree dendritic morphology are synthesized through simple anodization method, and the final product Sn/SnO\u003csub\u003e2\u003c/sub\u003e particles after different heat treatments show superior photocatalytic degradation of RhB under simulated solar light.\u003c/p\u003e","description":"","filename":"floatimage1.png","url":"https://assets-eu.researchsquare.com/files/rs-4270111/v1/ec990820e4fba4306361019e.png"}],"financialInterests":"No competing interests reported.","formattedTitle":"Electrochemically synthesized Tin micro-nanometer powders for visible light photocatalytic degradation of Rhodamine B dye from polluted water","fulltext":[{"header":"1 Introduction","content":"\u003cp\u003eTin (Sn) particles play an important role as electronic interconnect materials in electronic devices [\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e, \u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e]. As the demand for interconnection of components and fine-pitch printing is continuously increasing, Sn nanoparticles are considered as the most promising candidate for conductive inkjet printing material to replace traditional nano-silver [\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e, \u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e]. Sn nanoparticles have been received wide attention as one of the promising anode materials for lithium batteries, the results show that the theoretical value of its capacitance can be as high as 993 mA\u0026middot;h\u0026middot;g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, which is about three times that of carbon anode materials [\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e, \u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e]. Recently, in order to improve the performance of lithium-ion batteries performance, Sn and carbon nanocomposites have been reported with high capacity and capacity retention when used as anode materials [\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e, \u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e]. In addition, Sn nanoparticles exhibit excellent wear resistance, and compared to the size of particles formed in glasses with no or little Sn, it can accelerate the formation of gold clusters in silicate glasses and induce a reduction in the average size of gold nanoparticles [\u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eBased on the above knowledge, Sn nanomaterials have huge application prospects in many areas of human life, so the research on the preparation of nano-Sn is getting more and more attention from researchers. Various procedures have been proposed and applied to obtain Sn nanoparticles, such as mechanical alloying technology [\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e], arc discharge technology [\u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e], metal vapor condensation technology [\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e], liquid-phase reduction [\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e], physical vapor deposition (PVD) [\u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e], chemical liquid deposition (CLD) [\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e], electrochemical method [\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e], reverse micelle method [\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e] and so on. For example, Chee \u003cem\u003eet al\u003c/em\u003e. [\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e] used stannous octoate as a raw material, sodium borohydride as a reducing agent, and polyvinylpyrrolidone (PVP) as a surfactant to study the effects of reaction temperature, drying temperature, ultrasonic vibration, and centrifugal speed on the size of Sn nanoparticles. It was found that the size of Sn nanoparticles increased with the increase of reaction temperature and drying temperature, and the agglomeration of Sn nanoparticles was aggravated with the increase of ultrasonic and centrifugal speed [\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e]. However, in these methods, the Sn nanoparticles obtained by some methods are prone to agglomeration, results in uneven size and contains many impurities (such as mechanical alloying technology and arc discharge technology), some require reaction in a vacuum environment (such as PVD method), and some require harsh experimental conditions and complex operations (such as metal vapor condensation technology) [\u003cspan additionalcitationids=\"CR21\" citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e]. Only the electrochemical method based on electrolysis theory is simple in operation and low in cost, and it is easy to obtain Sn nanoparticles with controllable and uniform morphology by controlling the reaction conditions [\u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e, \u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eIn addition, semiconductor oxides play a huge role in the field of catalytic degradation due to their unique electron and hole characteristics [\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e]. Tin dioxide (SnO\u003csub\u003e2\u003c/sub\u003e) as an n-type wide bandgap semiconductor material, which is widely used in the cleaning and purification of organic pollutants in water and air due to its unique photocatalytic activity and good chemical stability [\u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e, \u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e]. Furthermore, as a photocatalyst, SnO\u003csub\u003e2\u003c/sub\u003e has mild reaction conditions, fast reaction speed, high catalytic activity, strong oxidation ability, low energy consumption, and no secondary pollution, so it is considered to be one of the most promising green catalysts [\u003cspan additionalcitationids=\"CR29\" citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e]. Elango et al. [\u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e31\u003c/span\u003e] synthesized SnO\u003csub\u003e2\u003c/sub\u003e nanoparticles by green method using \u003cem\u003ePersia Americana\u003c/em\u003e seed methanolic extract, it was found that the synthesized SnO\u003csub\u003e2\u003c/sub\u003e nanoparticles had a size of 4 nm and exhibited an excellent photocatalytic degradation effect on the organic dye phenolsulfonphthalein (phenol red).\u003c/p\u003e \u003cp\u003eIn this paper, Sn particles with a dendritic microstructure were generated at the cathode by a simple electrochemical anodic oxidation method, and then metal Sn-doped semiconductor SnO\u003csub\u003e2\u003c/sub\u003e hybrids with certain photocatalytic activity were obtained by further high-temperature oxidation treatment. With the help of SEM and XRD measurements, the morphologies and structures of the Sn and Sn/SnO\u003csub\u003e2\u003c/sub\u003e microparticles were characterized respectively. Specifically, the influencing parameters such as applied potential, electrolyte and its concentration were discussed, and the growth of process of Sn microparticles with dendritic structure was also discussed. Different ratio of Sn and SnO\u003csub\u003e2\u003c/sub\u003e in the final product was get after different heat treatment temperature. The final photocatalytic degradation experiment results found that the photocatalytic activity Sn/SnO\u003csub\u003e2\u003c/sub\u003e particles was superior to that of the pure Sn particles estimated with the degradation of rhodamine B (RhB) under simulated solar light.\u003c/p\u003e"},{"header":"2 Experimental procedures","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003e2.1 Materials\u003c/h2\u003e \u003cp\u003eHigh-purity tin flake (1000 \u0026times; 1000 \u0026times; 1 mm, 99.99%) and high-purity titanium flake (1000 \u0026times; 1000 \u0026times; 1 mm, 99.99%) were obtained from Beijing Jinyuan New Material Technology Co., Ltd. (Beijing, China). Ethanol (CH\u003csub\u003e3\u003c/sub\u003eCH\u003csub\u003e2\u003c/sub\u003eOH, 99.7%), acetone (CH\u003csub\u003e3\u003c/sub\u003eCOCH\u003csub\u003e3\u003c/sub\u003e, AR), isopropanol (C\u003csub\u003e3\u003c/sub\u003eH\u003csub\u003e8\u003c/sub\u003eO, AR) and methanol (CH\u003csub\u003e3\u003c/sub\u003eOH, AR) were purchased from Shanghai Aladdin Reagent Co., Ltd., China. Hydrofluoric acid (HF, AR, 40%), nitric acid (HNO\u003csub\u003e3\u003c/sub\u003e, AR), Ethylenediamine (C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e8\u003c/sub\u003eN\u003csub\u003e2\u003c/sub\u003e, AR) and ammonium fluoride (NH\u003csub\u003e4\u003c/sub\u003eF, AR, 98%) were provided by Shanghai McLean Biochemical Technology Co., Ltd., China. Rhodamine B (RhB) was supplied by Tianjin Bodi Chemical Reagent Co. Ltd. (AR, Tianjin, China). Distilled water was used throughout the experiments. All reagents were of analytical grade and used without further purification.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec4\" class=\"Section2\"\u003e \u003ch2\u003e2.2 Preparation of Sn particles and Sn/SnO\u003csub\u003e2\u003c/sub\u003e hybrid\u003c/h2\u003e \u003cp\u003eBefore anodization, it needs to clean and polish the Sn and Ti sheets. Specifically, the Sn sheets and Ti sheets cut into 2 cm \u0026times; 2 cm were sonicated in acetone, isopropanol and methanol for 10 min in turn. Then, the Sn sheet was physically polished with sandpaper, and the Ti sheet was chemically polished in a mixture of V(HF):V(HNO\u003csub\u003e3\u003c/sub\u003e):V(H\u003csub\u003e2\u003c/sub\u003eO)\u0026thinsp;=\u0026thinsp;1:4:5, and last cleaned with deionized water. Sn particles are obtained through a unique electrochemical method, the experiments were performed at the room temperature in a two-electrodes using Sn plate as the anode and Ti plate as the cathode. The electrolyte used was ethylene glycol solutions of NH\u003csub\u003e4\u003c/sub\u003eF which concentration was in the range from 0.04 M to 0.2 M. A constant voltage was applied for each experiment, ranging from 5 to 50 V. After electrochemical reaction for a period of time, the coating deposited on the cathode Ti sheet was collected. The products (Sn particles) were washed and centrifuged several times with distilled water and absolute ethanol respectively to remove the impurities, and then dried in a drying oven at 70\u0026deg;C. The Sn particles are subjected to different high-temperature (450 ℃, 550 ℃, and 600 ℃) oxidation treatments to obtain the corresponding Sn/SnO\u003csub\u003e2\u003c/sub\u003e hybrid.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec5\" class=\"Section2\"\u003e \u003ch2\u003e2.3 Characterization\u003c/h2\u003e \u003cp\u003eThe phases and structures of the prepared samples were measured with a Rigaku D/Max2500PC X-ray diffraction (XRD) equipped with graphite monochromatized Cu Kα radiation (λ\u0026thinsp;=\u0026thinsp;0.15418 nm), using a scanning rate of 4\u0026deg;\u0026middot;min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e in 2θ rage from 10\u0026deg; to 80\u0026deg;. The morphology of the products was characterized by a scanning electron microscope (SEM, SU-70) with acceleration voltage of 15 KV. The concentration of RhB in the solution was then measured by using a UV\u0026ndash;Vis spectrophotometer (UV9000) at a wavelength of 554 nm.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec6\" class=\"Section2\"\u003e \u003ch2\u003e2.4 Photocatalytic activity performance tests and electrochemical performance analysis\u003c/h2\u003e \u003cp\u003eThe photocatalytic activity of the product was evaluated through the photodegradation of Rhodamine B (RhB) under a simulated solar light irradiation. The experimental process could be summarized as follows: 0.05 g of the as-prepared samples were dispersed ultrasonically for 2 min in 50 mL of RhB solution with a concentration of 10 mg\u0026middot;L\u003csup\u003e\u0026ndash;1\u003c/sup\u003e. A 300 W xenon lamp without any optical filters was employed to simulate the solar light irradiation.\u003c/p\u003e \u003cp\u003eThe electrochemical performance (transient photocurrent density) of Sn/SnO\u003csub\u003e2\u003c/sub\u003e hybrid was detected by the three-electrode system of the electrochemical workstation (Autolab, Metrohm Co. Ltd.). Under the intermittent irradiation of Xenon lamp to simulate sunlight, a nickel foam (4 cm\u003csup\u003e2\u003c/sup\u003e) coated with 20 mg catalyst was used as working electrode, platinum electrode as counter electrode, saturated calomel electrode as reference electrode, and electrolyte selected as 0.1 mol/L Na\u003csub\u003e2\u003c/sub\u003eSO\u003csub\u003e4\u003c/sub\u003e solution.\u003c/p\u003e \u003c/div\u003e"},{"header":"3 Results and discussion","content":"\u003cdiv id=\"Sec8\" class=\"Section2\"\u003e \u003ch2\u003e3.1 Morphological characterization of Sn particles obtained under different conditions\u003c/h2\u003e \u003cp\u003eTin (Sn) particles generated at the cathode by electrochemical methods, the morphology and size of Sn microparticles can be controlled by adjusting the experimental conditions, such as composition of electrolyte (fluoride ion content, deionized water content), applied voltage, and reaction time [\u003cspan additionalcitationids=\"CR33\" citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e].\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eIn order to establish the impact of fluoride ion concentration on the micro-nano structure, we prepared samples by changing the NH\u003csub\u003e4\u003c/sub\u003eF content (0.04 mol/L, 0.08 mol/L, 0.15 mol/L, 0.20 mol/L, respectively) based on the consistency of other factors (deionized water content of 5 vol%, reaction voltage of 15 V and reaction time of 5 h). As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e, Sn particles present a unique dendritic morphology, and the shape of the dendrites is closely related to the concentration of NH\u003csub\u003e4\u003c/sub\u003eF. From the SEM of Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ea, it can be seen that at low NH\u003csub\u003e4\u003c/sub\u003eF content (0.04 mol/L), the obtained dendritic Sn particles are larger in size, the stems are slightly bent, and the whole morphology is rough and irregular. When the concentration of NH\u003csub\u003e4\u003c/sub\u003eF increased to 0.08 mol/L, the morphology of dendritic products tended to be regular, the stems tended to be straight and the length of branches decreased (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eb). When the NH\u003csub\u003e4\u003c/sub\u003eF concentration is further increased to 0.15 mol/L, the branches of dendritic Sn particles become finer and the stem length is decreases to 50 \u0026micro;m (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ec). When the NH\u003csub\u003e4\u003c/sub\u003eF content reaches 0.20 mol/L, large-grained dendrites appear, and the dendritic morphology becomes irregular and agglomerated (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ed). It can be concluded that the content of NH\u003csub\u003e4\u003c/sub\u003eF has a great influence on the morphology of tin micro-nano powder, and when its concentration is 0.15 mol/L, the perfect product of Sn dendrite can be obtained.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eNext, we analyzed the effect of the content of a small amount of deionized water in the electrolyte solution on the morphology of Sn micro-nanostructures. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ea and \u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eb, on the basis of other conditions being uniform (NH\u003csub\u003e4\u003c/sub\u003eF content of 0.15 mol/L, reaction voltage of 15 V and reaction time of 5 h), at low deionized water content (1.5 and 3 vol%), the dendritic Sn particles are irregular in shape and accompanied by many debris. When the deionized water content increased to 5 vol%, the crystal morphology of the obtained dendritic products tends to be regular and perfect, and the fine branches become numerous and dense (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ec). When the deionized water content is further increased to 10 vol%, the stem length of dendritic Sn particles increases, but the fine branches tend to be sparse (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ed).\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eFor the electrochemical reaction process, the applied voltage also has a great influence on the morphology of the deposited product on the electrode [\u003cspan citationid=\"CR35\" class=\"CitationRef\"\u003e35\u003c/span\u003e, \u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e36\u003c/span\u003e]. Figure\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e is the SEM of Sn microparticles obtained under different reaction voltages, from Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ea, after 5 h electrochemical reaction, the products obtained by applying a voltage of 5 V are mostly granular, and the dendritic morphology is not perfect. When the applied voltage increased to 10 V, the morphology of dendritic products gradually formed, but the thin branches are not completely bifurcation (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003eb). As the voltage continues to increase to 15 V and 30 V, it can be seen from Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ec and d that the morphology of dendritic Sn particles tends to be regular, and there is no obvious change in the SEM of 15 V and 30 V.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe growth process of Sn microparticles with dendritic structure was studied by controlling the reaction time. In order to explore the crystal growth of Sn particles, the growth process of the crystal product is studied from the nanometer size in a short time (5 min, 30 min, 60 min and 90 min). Under the condition of an applied voltage of 15 V, after the electrochemical reaction for 5 min, the Sn nanoparticles deposited on the cathode show a nano-dispersion state, and the Sn particle size is about 25 nm (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ea). When the reaction time reaches 30 min, the Sn nanoparticles grow to about 100 nm, but remain independent from each other (Fig .4b). From Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ec, as the reaction time is above 60 min, Sn nanoparticles grow further and some begin to connect and merge with each other. With the time increased to 90 min, for Sn nanoparticles with increasing size, the compatibility phenomenon is more obvious and the dendritic rudiment appears (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ed). Until the reaction time increases to 5 h, the Sn particles show a perfect dendritic morphology.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec9\" class=\"Section2\"\u003e \u003ch2\u003e3.2 Mechanism of electrochemical method to generate Sn particles\u003c/h2\u003e \u003cp\u003eCombining the growth morphology of Sn crystal products under different conditions above, and based on the theoretical basis for the preparation of metal particles by the electrochemical anodic oxidation-cathode precipitation method, we get that the formation mechanism of Sn particles is mainly divided into four stages.\u003c/p\u003e \u003cp\u003eIn the first stage, due to the hydrolysis of NH\u003csub\u003e4\u003c/sub\u003eF, the electrolyte is weakly acidic, during the electrolysis process [\u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e37\u003c/span\u003e], the Sn sheet as anode is oxidized, and many micro bubbles appear on the cathode Ti sheet. The main reactions of the two electrodes are as follows:\u003c/p\u003e \u003cp\u003eAnode: Sn \u0026rarr; Sn\u003csup\u003e2+\u003c/sup\u003e + 2e\u003csup\u003e\u0026minus;\u003c/sup\u003e (1)\u003c/p\u003e \u003cp\u003eCathode: 2H\u003csup\u003e+\u003c/sup\u003e + 2e\u003csup\u003e\u0026minus;\u003c/sup\u003e \u0026rarr; H\u003csub\u003e2\u003c/sub\u003e (2)\u003c/p\u003e \u003cp\u003eIn the second stage, the fluoride ion (F\u003csup\u003e\u0026minus;\u003c/sup\u003e) in the electrolyte solution is complexed with the tin ion (Sn\u003csup\u003e2+\u003c/sup\u003e) generated by the anode to obtain SnF\u003csub\u003e4\u003c/sub\u003e\u003csup\u003e2\u0026minus;\u003c/sup\u003e, and the specific reaction is:\u003c/p\u003e \u003cp\u003eSn\u003csup\u003e2+\u003c/sup\u003e + 4F\u003csup\u003e\u0026minus;\u003c/sup\u003e \u0026rarr; SnF\u003csub\u003e4\u003c/sub\u003e\u003csup\u003e2\u0026minus;\u003c/sup\u003e (3)\u003c/p\u003e \u003cp\u003eIn the third stage, the SnF\u003csub\u003e4\u003c/sub\u003e\u003csup\u003e2\u0026minus;\u003c/sup\u003e reach the vicinity of the cathode under the action of magnetic stirring and are reduced to metal Sn particles by obtaining electrons, the reaction is as follows:\u003c/p\u003e \u003cp\u003eSnF\u003csub\u003e4\u003c/sub\u003e\u003csup\u003e2\u0026minus;\u003c/sup\u003e + 2e\u003csup\u003e\u0026minus;\u003c/sup\u003e \u0026rarr; Sn\u0026thinsp;+\u0026thinsp;4F\u003csup\u003e\u0026minus;\u003c/sup\u003e (4)\u003c/p\u003e \u003cp\u003eIn the fourth stage, when the metal Sn crystal nucleus starts to precipitate on the cathode, as the reaction proceeds, the Sn particles gradually grow and become larger in size, and with the different reaction conditions, the morphology of the obtained Sn particles is also different.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec10\" class=\"Section2\"\u003e \u003ch2\u003e\u003cb\u003e3.3 Characterization analysis of Sn/SnO\u003c/b\u003e\u003csub\u003e\u003cb\u003e2\u003c/b\u003e\u003c/sub\u003e \u003cb\u003eafter Sn particles treated at different high temperatures\u003c/b\u003e\u003c/h2\u003e \u003cp\u003eBy exploring the influence of different conditions on the crystal morphology, the optimal conditions for the electrochemical method to prepare Sn particles are obtained: in the ethylene glycol electrolyte solution containing NH\u003csub\u003e4\u003c/sub\u003eF, the content of NH\u003csub\u003e4\u003c/sub\u003eF is 0.15 mol/L, the deionized water content was 5 vol%, and the reaction is carried out for 5 h under the applied working voltage of 15 V. In order to make the product have higher photocatalytic activity, the Sn particles with dendritic crystal morphology were then subjected to high-temperature calcination treatment at 450\u0026deg;C, 550\u0026deg;C and 600\u0026deg;C, respectively [\u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e38\u003c/span\u003e, \u003cspan citationid=\"CR39\" class=\"CitationRef\"\u003e39\u003c/span\u003e], and the SEM of the obtained samples are shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ea-c. Compared with the Sn particles, the morphology of the samples changed after high temperature treatment. It can be seen from Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ea that when the temperature is set at 450\u0026deg;C, the surface of the sample is scattered due to oxidation, but the overall dendritic skeleton morphology remains unchanged. When the heat treatment temperature increased to 550\u0026deg;C, the branches of dendritic Sn particles gathered together and a large number of micropores appeared on the surface with the intensification of the oxidation degree (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003eb). When the temperature reaches 600\u0026deg;C, it can be seen from Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ec that the dendritic morphology of the sample becomes less obvious, and the surface tends to be loose and porous. In summary, it can be concluded that the morphology of the Sn particles obtained by the electrochemical method changes from a regular dendritic structure to a loose and porous structure after different high-temperature treatments, which provides abundant catalytic active sites for the obtained samples as photocatalysts [\u003cspan citationid=\"CR40\" class=\"CitationRef\"\u003e40\u003c/span\u003e, \u003cspan citationid=\"CR41\" class=\"CitationRef\"\u003e41\u003c/span\u003e].\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eTo analyze the crystal structure and phase composition of the as-prepared samples after high-temperature treatment, XRD was carried out. The XRD patterns of the as-prepared products are shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ed. For the obtained Sn particles, all the diffraction peaks are in well agreement with the literature values of the tetragonal phase of metallic Sn (JCPDS No.04-0673) [\u003cspan additionalcitationids=\"CR43\" citationid=\"CR42\" class=\"CitationRef\"\u003e42\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR44\" class=\"CitationRef\"\u003e44\u003c/span\u003e]. Nearly no other peaks of impurities are detected, showing that the obtained Sn particles are of high purity. After Sn microparticles are treated at different high temperatures (450 ℃, 550 ℃ and 600 ℃), the peaks of cassiterite SnO\u003csub\u003e2\u003c/sub\u003e (JCPDS file No. 41-1445) can be also found in the patters [\u003cspan additionalcitationids=\"CR46\" citationid=\"CR45\" class=\"CitationRef\"\u003e45\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR47\" class=\"CitationRef\"\u003e47\u003c/span\u003e]. Therefore, the main component of the sample obtained after high temperature treatment is the hybrid compound composed of Sn and n-type semiconductor SnO\u003csub\u003e2\u003c/sub\u003e (Sn/SnO\u003csub\u003e2\u003c/sub\u003e). It is worth noting that with the increase of heat treatment temperature, the diffraction peak of metal Sn in the hybrid gradually weakens, and the characteristic peak of SnO\u003csub\u003e2\u003c/sub\u003e gradually increases, indicating that the oxidation degree of Sn particles deepens with the increase of temperature.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec11\" class=\"Section2\"\u003e \u003ch2\u003e3.4 Photocatalytic performance of Sn/SnO\u003csub\u003e2\u003c/sub\u003e\u003c/h2\u003e \u003cp\u003en-type semiconductor SnO\u003csub\u003e2\u003c/sub\u003e has excellent stability and photocatalytic activity [\u003cspan additionalcitationids=\"CR49\" citationid=\"CR48\" class=\"CitationRef\"\u003e48\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR50\" class=\"CitationRef\"\u003e50\u003c/span\u003e]. In this work, the Sn/SnO\u003csub\u003e2\u003c/sub\u003e hybrid with metal Sn-doped semiconductor SnO\u003csub\u003e2\u003c/sub\u003e properties obtained by high-temperature treatment of dendritic Sn particles can further improve the photocatalytic performance of traditional catalyst SnO\u003csub\u003e2\u003c/sub\u003e [\u003cspan citationid=\"CR51\" class=\"CitationRef\"\u003e51\u003c/span\u003e, \u003cspan citationid=\"CR52\" class=\"CitationRef\"\u003e52\u003c/span\u003e]. To eliminate the effect of adsorption on photocatalysis, for each experiment, 50 mg of catalyst powder was added to 50 mL of RhB solution and stirred for 1 h in the dark to obtain adsorption/desorption equilibrium [\u003cspan citationid=\"CR53\" class=\"CitationRef\"\u003e53\u003c/span\u003e]. During light irradiation, the catalyst was kept in suspension by a magnetic stirrer, and 2 ml of the reaction solution was aspirated with a pipette every 30 min and centrifuged immediately to separate the catalyst from the solution. Finally, the concentration of RhB in the solution after a fixed time was measured at a wavelength of 554 nm by a UV-visible spectrophotometer [\u003cspan citationid=\"CR54\" class=\"CitationRef\"\u003e54\u003c/span\u003e]. The specific degradation efficiency calculation formula is as follows [\u003cspan citationid=\"CR55\" class=\"CitationRef\"\u003e55\u003c/span\u003e]:\u003c/p\u003e \u003cp\u003eThe degradation efficiency = [(\u003cem\u003eC\u003c/em\u003e\u003csub\u003e\u003cem\u003e0\u003c/em\u003e\u003c/sub\u003e-\u003cem\u003eC\u003c/em\u003e\u003csub\u003e\u003cem\u003et\u003c/em\u003e\u003c/sub\u003e)/\u003cem\u003eC\u003c/em\u003e\u003csub\u003e0\u003c/sub\u003e] \u0026times; 100% (5)\u003c/p\u003e \u003cp\u003ewhere \u003cem\u003eC\u003c/em\u003e\u003csub\u003e\u003cem\u003e0\u003c/em\u003e\u003c/sub\u003e is the initial concentration of RhB, \u003cem\u003eC\u003c/em\u003e\u003csub\u003e\u003cem\u003et\u003c/em\u003e\u003c/sub\u003e is the concentration of RhB at time \u003cem\u003et\u003c/em\u003e. From Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ea, after illumination for 5 h, compared with commercial SnO\u003csub\u003e2\u003c/sub\u003e, the photocatalytic efficiency of the Sn/SnO\u003csub\u003e2\u003c/sub\u003e hybrid obtained in this work has been greatly improved, especially for the degradation efficiency of the catalyst obtained by calcination at 550\u0026deg;C as high as 89.8%. It is worth noting that when the calcination temperature continues to increase to 600\u0026deg;C, the photocatalytic efficiency of the hybrids decreases, which may be related to the electron mismatch in the Sn and SnO\u003csub\u003e2\u003c/sub\u003e heterojunction.\u003c/p\u003e \u003cp\u003eIn order to verify the accuracy of the above photocatalytic efficiency and predict that the degradation of RhB by the catalyst may be related to the rapid interfacial transfer of photogenerated charge carriers and the subsequent effective charge separation, the photocurrent response behavior of the sample electrode in 0.1M Na\u003csub\u003e2\u003c/sub\u003eSO\u003csub\u003e4\u003c/sub\u003e electrolyte under intermittent visible light irradiation was tested using a three-electrode system in an electrochemical workstation [\u003cspan citationid=\"CR56\" class=\"CitationRef\"\u003e56\u003c/span\u003e, \u003cspan citationid=\"CR57\" class=\"CitationRef\"\u003e57\u003c/span\u003e]. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003eb, the prepared electrodes of different samples have a very obvious change in the response current under the condition of intermittent switching of the xenon lamp for 15 s. The Sn/SnO\u003csub\u003e2\u003c/sub\u003e (550\u0026deg;C) electrode demonstrated a stronger transient photocurrent response (0.38 mA/cm\u003csup\u003e2\u003c/sup\u003e) under visible light illumination, which was higher than that of commercial SnO\u003csub\u003e2\u003c/sub\u003e (0.26 mA/cm\u003csup\u003e2\u003c/sup\u003e), Sn/SnO\u003csub\u003e2\u003c/sub\u003e (450\u0026deg;C) (0.33 mA/cm\u003csup\u003e2\u003c/sup\u003e), and Sn/SnO\u003csub\u003e2\u003c/sub\u003e (600\u0026deg;C) (0.36 mA/cm\u003csup\u003e2\u003c/sup\u003e). In addition, after three cycles of light cycles, the current density under light conditions is basically constant, which proves that the prepared catalyst has good stability.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eIn order to more directly reflect the photocatalytic performance of the catalyst on RhB in different time periods, the time-dependent UV-Vis absorption spectrum of RhB with Sn/SnO\u003csub\u003e2\u003c/sub\u003e (550\u0026deg;C) electrode is also operated and shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ec. It can be clearly seen from the figure that with the passage of degradation time, the UV-Vis absorption peak intensity of RhB in the solution decreased significantly at 554 nm. The recycling performance of photocatalysts is considered to be a key factor for evaluating the green sustainable catalysts, the cyclic experiments of Sn/SnO\u003csub\u003e2\u003c/sub\u003e (550\u0026deg;C) are conducted for seven runs and the result is depicted in Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ed. After the first measurement, the catalyst is centrifuged, washed three times with deionized water and ethanol, and dried for the next cycle experiment. From the experimental results, it can be found that the degradation efficiency of the catalyst Sn/SnO\u003csub\u003e2\u003c/sub\u003e (550\u0026deg;C) to RhB can still achieve more than 80.0% after 5 cycles, and the degradation efficiency decreases but still remains above 70.0% after 7 cycles. The degradation of performance may be related to the surface deactivation caused by the adsorption of RhB degradation products to the surface of the catalyst. Therefore, these results indicate that the photocatalyst obtained in this study has good reusability.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec12\" class=\"Section2\"\u003e \u003ch2\u003e3.5 Photocatalytic mechanism of Sn/SnO\u003csub\u003e2\u003c/sub\u003e\u003c/h2\u003e \u003cp\u003eThe above results indicate that the Sn doped SnO\u003csub\u003e2\u003c/sub\u003e samples have shown much improved photocatalytic activity on the photodegradation of RhB than the pure commercial SnO\u003csub\u003e2\u003c/sub\u003e. The UV-vis diffuse reflectance spectra of the pure SnO\u003csub\u003e2\u003c/sub\u003e and calcined sample Sn/SnO\u003csub\u003e2\u003c/sub\u003e are showed in Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003ea, it can be clearly seen that Sn/SnO\u003csub\u003e2\u003c/sub\u003e have good light absorption than pure SnO\u003csub\u003e2\u003c/sub\u003e in the visible light absorption range with a range of 400\u0026ndash;750 nm, which indicates that doped Sn enhanced significantly visible light absorption of SnO\u003csub\u003e2\u003c/sub\u003e catalyst. The direct band gap (\u003cem\u003eE\u003c/em\u003e\u003csub\u003e\u003cem\u003eg\u003c/em\u003e\u003c/sub\u003e) values of different catalysts are estimated from the (\u003cem\u003eAhν\u003c/em\u003e)\u003csup\u003e2\u003c/sup\u003e versus photon energy (\u003cem\u003ehν\u003c/em\u003e) plot as showed in the Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003eb [\u003cspan citationid=\"CR58\" class=\"CitationRef\"\u003e58\u003c/span\u003e]. As depicted in Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003eb, the band gap of Sn/SnO\u003csub\u003e2\u003c/sub\u003e have been narrowed from 3.85 eV (pure SnO\u003csub\u003e2\u003c/sub\u003e) to 3.82 (calcined at 450\u0026deg;C), 3.76 (calcined at 550\u0026deg;C) and 3.80eV (calcined at 600\u0026deg;C), respectively. It is worth mentioning that the band gap of samples obtained at 550\u0026deg;C is the lowest and the photocatalytic effect is the best. The surface is attributed to the unique morphology to provide abundant active sites. The deep theory is that the appropriate amount of Sn-doped SnO\u003csub\u003e2\u003c/sub\u003e catalyst obtained at 550\u0026deg;C promotes the transfer of photogenerated charge and extends the lifespan of photogenerated charge.\u003c/p\u003e \u003cp\u003eThe probable photocatalytic mechanism of Sn-doped SnO\u003csub\u003e2\u003c/sub\u003e hierarchical structures for degradation of RhB and schematic electronic structure for significantly improving photocatalytic performance are illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003ec. Under visible light excitation, electrons in the valence band (VB) of Sn-doped SnO\u003csub\u003e2\u003c/sub\u003e catalyst can be excited to the conduction band (CB) of the catalyst, while forming the same number of holes in VB (Eqs.\u0026nbsp;(6)), leading to the formation of photogenerated electron\u0026ndash;hole pairs [\u003cspan citationid=\"CR59\" class=\"CitationRef\"\u003e59\u003c/span\u003e, \u003cspan citationid=\"CR60\" class=\"CitationRef\"\u003e60\u003c/span\u003e]. Compared to pure SnO\u003csub\u003e2\u003c/sub\u003e, the Sn-doped SnO\u003csub\u003e2\u003c/sub\u003e hierarchical structure shows the stronger light absorption and lower band gap and the, therefore, more charge carriers can be excited in the process and then participate in following photocatalytic reactions [\u003cspan citationid=\"CR61\" class=\"CitationRef\"\u003e61\u003c/span\u003e, \u003cspan citationid=\"CR62\" class=\"CitationRef\"\u003e62\u003c/span\u003e]. The reactive electrons (e\u003csup\u003e\u0026minus;\u003c/sup\u003e) from the Sn/SnO\u003csub\u003e2\u003c/sub\u003e reduce O\u003csub\u003e2\u003c/sub\u003e to\u0026middot;O\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e\u0026bull; \u0026minus;\u003c/sup\u003e (Eqs.\u0026nbsp;(7)) [\u003cspan citationid=\"CR63\" class=\"CitationRef\"\u003e63\u003c/span\u003e]. Meanwhile, the reactive holes (h\u003csup\u003e+\u003c/sup\u003e) oxidize RhB to its radical cation either directly (Eqs.\u0026nbsp;(10)) or through a primarily formed \u003csup\u003e\u0026bull;\u003c/sup\u003eOH produced by the oxidation of ubiquitous water (Eqs.\u0026nbsp;(8)) [\u003cspan citationid=\"CR64\" class=\"CitationRef\"\u003e64\u003c/span\u003e, \u003cspan citationid=\"CR65\" class=\"CitationRef\"\u003e65\u003c/span\u003e]. O\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e\u0026bull; \u0026minus;\u003c/sup\u003e and \u003csup\u003e\u0026bull;\u003c/sup\u003eOH are proven to be the main active species, which can eventually convert organic dyes (RhB) into CO\u003csub\u003e2\u003c/sub\u003e, H\u003csub\u003e2\u003c/sub\u003eO and others (Eqs.\u0026nbsp;(9) and (11)) [\u003cspan citationid=\"CR66\" class=\"CitationRef\"\u003e66\u003c/span\u003e].\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"No\" id=\"Taba\" border=\"1\"\u003e \u003ccolgroup cols=\"2\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eSn/SnO\u003csub\u003e2\u003c/sub\u003e\u0026thinsp;+\u0026thinsp;visible light \u0026rarr;Sn/SnO\u003csub\u003e2\u003c/sub\u003e\u0026thinsp;+\u0026thinsp;e\u003csup\u003e\u0026minus;\u003c/sup\u003e\u003csub\u003e(CB)\u003c/sub\u003e\u0026thinsp;+\u0026thinsp;h\u003csup\u003e+\u003c/sup\u003e\u003csub\u003e(CB)\u003c/sub\u003e\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003e (6)\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003ee\u003csup\u003e\u0026minus;\u003c/sup\u003e + O\u003csub\u003e2\u003c/sub\u003e \u0026rarr; O\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e\u0026bull; \u0026minus;\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e (7)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eh\u003csup\u003e+\u003c/sup\u003e + H\u003csub\u003e2\u003c/sub\u003eO \u0026rarr; \u003csup\u003e\u0026bull;\u003c/sup\u003eOH\u0026thinsp;+\u0026thinsp;H\u003csup\u003e+\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e(8)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eRhB\u0026thinsp;+\u0026thinsp;O\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e\u0026bull; \u0026minus;\u003c/sup\u003e \u0026rarr; CO\u003csub\u003e2\u003c/sub\u003e\u0026thinsp;+\u0026thinsp;H\u003csub\u003e2\u003c/sub\u003eO\u0026thinsp;+\u0026thinsp;Other products\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e(9)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eRhB\u0026thinsp;+\u0026thinsp;h\u003csup\u003e+\u003c/sup\u003e \u0026rarr; CO\u003csub\u003e2\u003c/sub\u003e\u0026thinsp;+\u0026thinsp;H\u003csub\u003e2\u003c/sub\u003eO\u0026thinsp;+\u0026thinsp;Other products\u003c/p\u003e \u003cp\u003eRhB + \u003csup\u003e\u0026bull;\u003c/sup\u003eOH \u0026rarr; CO\u003csub\u003e2\u003c/sub\u003e\u0026thinsp;+\u0026thinsp;H\u003csub\u003e2\u003c/sub\u003eO\u0026thinsp;+\u0026thinsp;Other products\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e(10)\u003c/p\u003e \u003cp\u003e(11)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e"},{"header":"4 Conclusions","content":"\u003cp\u003eSn microparticles with dendritic structure were successfully synthesized from the cathode via a simple electrochemical method. It was found through SEM that the morphology and size of Sn particles were related to the experimental parameters, including composition of electrolyte (fluoride ion content, deionized water content), applied voltage, and reaction time. As a result, the optimal conditions for the electrochemical method to prepare dendritic Sn particles: in the ethylene glycol electrolyte solution containing NH\u003csub\u003e4\u003c/sub\u003eF, the content of NH\u003csub\u003e4\u003c/sub\u003eF is 0.15 mol/L, the deionized water content was 5 vol%, and the reaction is carried out for 5 h under the applied working voltage of 15 V. Then dendritic Sn particles were subjected to high-temperature calcination to obtain products that not only had numerous microporous morphology, but also contained hybrid phases of Sn and SnO\u003csub\u003e2\u003c/sub\u003e. The abundant catalytic active sites on the surface of the product and the characteristics of Sn-doped P-type semiconductor SnO\u003csub\u003e2\u003c/sub\u003e make it an excellent photocatalyst. Especially when the calcination temperature is 550\u0026deg;C, the Sn/SnO\u003csub\u003e2\u003c/sub\u003e product shows superior photocatalytic activity to other samples toward the degradation of RhB. In conclusion, this work provides a new strategy for the effective degradation of architecture and industrial dyes by a simple electrochemical method.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eDeclaration of competing interest\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe authors declare that they have no competing financial interests or personal relationships that could have influenced the work reported in this paper.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAcknowledgements\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe authors extend their appreciation to Taif University, Saudi Arabia for supporting this work through project number (TU-DSPP-2024-01).\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAuthor contribution\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eYukun Lu prepared the materials and conducted most of the measurements and data analysis. Yaojie Zhang and Jiale Zhang contributed to the data analysis. Zhaoyang Li, Feiyang Hu and Duo Pan conceived the idea, wrote the paper, and coordinated the overall project. Saad Melhi and Xuetao Shi revised the paper. Mohammed A. Amin provided supervision and resources. Zeinhom M. El-Bahy reviewed and revised the manuscript. All authors reviewed the manuscript.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eFunding\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eNone.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eData availability\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe authors confirm that the data supporting the findings of this study are available within the article. Raw data that support the findings of this study are available from the corresponding author, upon reasonable request.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eZou C-D, Gao Y-L, Bin Y, Zhai Q-J (2010) Size-dependent melting properties of Sn nanoparticles by chemical reduction synthesis. 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Adv Compos Hybrid Mater 5:1423\u0026ndash;1432. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1007/s42114-022-00520-4\u003c/span\u003e\u003cspan address=\"10.1007/s42114-022-00520-4\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"advanced-composites-and-hybrid-materials","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"achm","sideBox":"Learn more about [Advanced Composites and Hybrid Materials](https://link.springer.com/journal/42114)","snPcode":"42114","submissionUrl":"https://submission.nature.com/new-submission/42114/3","title":"Advanced Composites and Hybrid Materials","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"Tin micro-nanoparticles, morphology, Sn/SnO2 hybrid materials, Photocatalytic activity","lastPublishedDoi":"10.21203/rs.3.rs-4270111/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-4270111/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eTin (Sn) micro-nanoparticles with special pine tree dendritic morphology were synthesized by using tin foil as the anode and titanium as the cathode through simple anodization method. Surprisingly, it is found that the morphology of Sn particles is closely related to factors such as the type of electrolyte, the concentration of the electrolyte, and the different applied voltages, and briefly discussed the influence of various factors on the growth of Sn particles. In addition, Sn particles are calcined under different temperature conditions to obtain Sn/SnO\u003csub\u003e2\u003c/sub\u003e hybrid materials with different tin dioxide (SnO\u003csub\u003e2\u003c/sub\u003e) contents. The changes in morphology and the phase of SnO\u003csub\u003e2\u003c/sub\u003e crystal lattices were characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD), respectively, which proved the successful synthesis of Sn/SnO\u003csub\u003e2\u003c/sub\u003e mixed materials. Finally, the Sn/SnO\u003csub\u003e2\u003c/sub\u003e hybrid material with metal-doped modified semiconductor properties was used to photocatalytic degradation of simulated organic pollutants rhodamine B (RhB). It was found that the photocatalytic degradation efficiency of the Sn/SnO\u003csub\u003e2\u003c/sub\u003e hybrid material under simulated sunlight conditions is near 90% in 5 h. Therefore, this work provides a convenient and effective environmental protection approach for the treatment of architecture and industrial dyes.\u003c/p\u003e","manuscriptTitle":"Electrochemically synthesized Tin micro-nanometer powders for visible light photocatalytic degradation of Rhodamine B dye from polluted water","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2024-04-29 13:01:08","doi":"10.21203/rs.3.rs-4270111/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Revision requested","date":"2024-05-05T05:13:14+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2024-05-04T18:24:55+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"81c58013-4283-43e1-9a7d-ddfa1a69cb0b","date":"2024-05-04T18:00:58+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2024-05-03T18:54:16+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2024-05-03T14:17:10+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"43a79a52-6c95-4569-b7b6-b0fc5791551a","date":"2024-04-26T13:27:53+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"652ec1d0-3bdc-437b-9c01-8e32dfb714e2","date":"2024-04-24T16:00:00+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2024-04-24T08:23:34+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2024-04-24T07:22:23+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2024-04-19T01:32:13+00:00","index":"","fulltext":""},{"type":"submitted","content":"Advanced Composites and Hybrid Materials","date":"2024-04-15T13:35:57+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"advanced-composites-and-hybrid-materials","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"achm","sideBox":"Learn more about [Advanced Composites and Hybrid Materials](https://link.springer.com/journal/42114)","snPcode":"42114","submissionUrl":"https://submission.nature.com/new-submission/42114/3","title":"Advanced Composites and Hybrid Materials","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"e0ea7069-a048-4d03-b1a6-b65fa8caee7e","owner":[],"postedDate":"April 29th, 2024","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"under-review","subjectAreas":[],"tags":[],"updatedAt":"2024-06-14T00:23:25+00:00","versionOfRecord":[],"versionCreatedAt":"2024-04-29 13:01:08","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-4270111","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-4270111","identity":"rs-4270111","version":["v1"]},"buildId":"qtupq5eGEP_6zYnWcrvyt","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}