Silver iodide decorated Bi12O17Cl2 heterojunction with enriched oxygen vacancies toward efficiently enhanced mineralization of antibiotics

Silver iodide decorated Bi12O17Cl2 heterojunction with enriched oxygen vacancies toward efficiently enhanced mineralization of antibiotics | Authorea try { document.documentElement.classList.add('js'); } catch (e) { } var _gaq = _gaq || []; _gaq.push(['_setAccount', 'G-8VDV14Y67G']); _gaq.push(['_trackPageview']); (function() { var ga = document.createElement('script'); ga.type = 'text/javascript'; ga.async = true; ga.src = ('https:' == document.location.protocol ? 'https://ssl' : 'http://www') + '.google-analytics.com/ga.js'; var s = document.getElementsByTagName('script')[0]; s.parentNode.insertBefore(ga, s); })(); Skip to main content Preprints Collections Wiley Open Research IET Open Research Ecological Society of Japan All Collections About About Authorea FAQs Contact Us Quick Search anywhere Search for preprint articles, keywords, etc. Search Search ADVANCED SEARCH SCROLL This is a preprint and has not been peer reviewed. Data may be preliminary. 2 January 2025 V1 Latest version Share on Silver iodide decorated Bi12O17Cl2 heterojunction with enriched oxygen vacancies toward efficiently enhanced mineralization of antibiotics Authors : Zhaoyang Yan , Jun Ke 0000-0002-3734-5729 [email protected] , Yixuan Hu , Lulu Zhao , Jie Yan , and Ranxing Wang Authors Info & Affiliations https://doi.org/10.22541/au.173578705.53404164/v1 168 views 89 downloads Contents Abstract Information & Authors Metrics & Citations View Options References Figures Tables Media Share Abstract Herein, a novel 2D/0D Bi 12 O 17 Cl 2 /AgI (B 12 OC/AgI) heterojunction with enriched oxygen vacancies was synthesized via an in-situ growth method for enhanced mineralization performance of antibiotics. It was confirmed that owing to the formation of type II heterojunction between Bi enriched Bi 12 O 17 Cl 2 and AgI, the spatial separation of photoinduced electrons and holes was improved efficiently, thereby promoting the utilization rate of photogenerated charge carriers. As a result, the B 12 OC/AgI-15 exhibited the best degradation performance and the degradation efficiency of TC within 15 min was 95.02%. The corresponding kinetic constants of B 12 OC/AgI-15 to TC were 4.30 and 9.63 times higher than that of bare Bi 12 O 17 Cl 2 and AgI, respectively. Moreover, it was found that the combination of Bi 12 O 17 Cl 2 and AgI can effectively prevent the coupling of photoelectrons with interstitial Ag + to form metal Ag, which can improve the anti-photocorrosion ability and ensure structure stability of B 12 OC/AgI heterojunction. In addition, the intermediates and degradation pathways of TC over the B 12 OC/AgI were discussed in detail. 1. Introduction Tetracycline hydrochloride (TC) is considered one of the most important broad-spectrum antibiotics that inhibits protein synthesis in bacteria in addition to fighting various bacterial infections [1]. Therefore, it is widely used in medicine [2], animal husbandry [3] and aquaculture [4]. However, long-term excessive use of TC can lead to its accumulation in water environments such as urban groundwater [5], surface water [6] and drinking water [7], as well as the transmission of resistance genes in the environment [8]. At the same time, the high chemical stability of TC itself makes the current methods of degrading TC generally have the problems of low efficiency and high cost [9]. Therefore, it is of great practical significance to establish effective TC removal technology in water bodies. At present, various chemical, physical and biological methods have been used to remove TC, including filtration [10], adsorption [11], and advanced oxidation [12], of which advanced oxidation includes electrocatalysis [13], photocatalysis [14], persulfate activation [15], and piezoelectric catalysis [16]. Among them, photocatalytic technology is considered to be a promising antibiotic degradation method due to its high efficiency, low cost, and non-pollution [17]. Up to data, many semiconductors have been widely studied, such as TiO 2 [18], ZnO [19], Fe 3 O 4 [20], CdS [21], MoS 2 [22], and so on. Among the many photocatalytic materials, layered bismuth-based materials (BBCs) show great potential for the production of H 2 O 2 due to the tunable interlayer elements and the diversity of Bi 3+ and O 2- bonding methods (bond number, bond length, etc.). Bismuth and oxygen-enriched bismuth-oxyhalide (Bi 12 O 17 Cl 2 ) has a unique and attractive structure, in which the bonding mode and bond length of Bi 3+ and O 2- were analyzed in detail. In the Bi 12 O 17 Cl 2 structure, van der Waals force bonding occurs between [Bi 3 O 4.25 ] and [Cl] in the direction of [001], which is one more [BiO 2.25 ] than BiOCl. On this basis not only is the number of bonds greatly increased, but the direction of bond formation also shows greater variability. The bond length of Bi-O in BiOCl is 2.338 Å. Different from the BiOCl, the bond length of Bi-O in Bi 12 O 17 Cl 2 varies significantly from 1.943 to 2.529 Å, further leading to the structural asymmetry [23]. Density functional theory (DFT) theoretical calculations demonstrated that the presence of [Bi 3 O 4.25 ] converted the composition of the valence band from the original Cl 3p orbital to the O 2p orbital, which can make full use of the holes generated by piezoelectricity and resist oxidative inactivation. Meanwhile, the [Bi 3 O 4.25 ] part in the Bi 12 O 17 Cl 2 crystal can provide sufficient and stable adsorption and activation sites. These advantages make Bi 12 O 17 Cl 2 used widely in the field of photocatalytic degradation of pollutants [24]. However, the photocatalytic activity of Bi 12 O 17 Cl 2 is still limited by high recombination rate of photogenerated electrons and holes [25]. In order to overcome these shortcomings, many strategies such as crystal plane manipulation [25], regulation of oxygen vacancies [26], metal doping [27], and construction of heterojunctions [28] have been conducted to eliminate these negative effects. It is well demonstrated that the construction of heterojunction can increase the utilization efficiency of solar energy, hinder recombination of photogenerated electron-hole pairs, and thereby enhance the photocatalytic ability. Silver iodide (AgI) has attracted much attention due to good conductivity and visible light absorption, and suitable band gap of about 2.80 eV [29]. As a member of silver halide, AgI has a more negative conduction band potential than most of semiconductor materials, which can facilitate to form heterojunction and effectively promote the separation of carriers once loaded on the surface of other catalysts [30]. Therefore, it is often used to construct novel visible light-driven photocatalysts in conjunction with other semiconductor photocatalysts. For example, Xin et al. compounded AgI with ZrTiO 4 to form S-type heterojunction, which significantly improved the degradation efficiency of norfloxacin [31]. Besides, Zeng et al. designed a highly selective photoelectrochemical sensor for H 2 S detection using the high-efficiency photocurrent response rate of the g-C 3 N 4 /Ag/AgI heterojunction [32]. On the other hand, the AgI is easily decomposed and reduced to produce metallic Ag under light irradiation, causing unstable and non-reusable of AgI that is the undesirable photo corrosion effect. Therefore, the formation of heterojunction can to some degree guide photoinduced electrons to lower conduction band and efficiently suppress the reduction reaction of Ag + to Ag 0 . Based on this strategy, in this paper, the 3D/0D nanostructured Bi 12 O 17 Cl 2 /AgI heterojunction was successfully prepared by in-situ deposition method. The photocatalytic degradation performance of the Bi 12 O 17 Cl 2 /AgI composite was investigated by using tetracycline hydrochloride as target pollutant under visible light illumination. In addition, the crystal structure, morphology, size and photoelectric properties of the materials were studied by various characterization methods. Finally, based on results of free radical capture experiment, electrochemical test and energy band structure, the possible mechanism of photocatalytic degradation and the degradation pathway of tetracycline hydrochloride were proposed. 2. Experimental 2.1 Materials Bismuth nitrate pentahydrate (Bi(NO 3 ) 3 ·5H 2 O), glacial acetic acid (C 2 H 4 O 2 ), potassium chloride (KCl), sodium hydroxide (NaOH), silver nitrate (AgNO 3 ), potassium iodide (KI). The experimental drugs are purchased from Sinopharm Chemical Reagent Co., Ltd., and all chemical reagents are analytical grade and can be Scheme 1 Synthesis path of 0D/3D Bi 12 O 17 Cl 2 / AgI heterojunction. used without further purification. 2.2 Preparation of bismuth and oxygen-enriched bismuth-oxyhalide (Bi 12 O 17 Cl 2 ) 10 mL of glacial acetic acid and 6 mmol of Bi(NO 3 ) 3 ·5H 2 O were added into 20 mL of deionized water, and stirred well for 10 min until the solution is clarified. Then 10 mL of KCl (0.015g/mL) solution was added drop by drop and stirred for 1 h. Subsequently, the NaOH solution was used to adjust the solution to pH=6 and stirred for 2 h. After that, the precipitation was centrifugated and washed with water and ethanol alternately for several times, and then dried in the oven at 60 ℃ for 12 h. Finally, the precipitation precursor was calcined in Muffle furnace at 400 ℃ for 2 h with a heating rate of 5 ℃/min. 2.3 Preparation of Bi 12 O 17 Cl 2 /AgI heterojunction The detailed schematic diagram of the fabrication process of Bi 12 O 17 Cl 2 /AgI heterojunction was shown in Scheme 1 . In a typical procedure, 0.5 g of the obtained Bi 12 O 17 Cl 2 , certain amount of AgNO 3 , and 30 mL of deionized water were mixed and sonicated for 20 min. Then, a certain amount of KI solution was evenly dripped and stirred at room temperature for 3 h. Finally, the sample was centrifugated washed alternately with water and ethanol, and dried at 60 ℃ for 12 h. The Bi 12 O 17 Cl 2 /AgI composites with different amounts of AgI were synthesized by varying the addition of AgNO 3 and KI, where the mass ratios of AgI to Bi 12 O 17 Cl 2 were equal to 5%, 10%, 15%, 25% and 35% and the samples were recorded as B 12 OC/AgI-5, B 12 OC/AgI-10, B 12 OC/AgI-15, B 12 OC/AgI-25 and B 12 OC/AgI-35, respectively. Furthermore, for comparison, pure AgI was prepared by using the same method without addition of Bi 12 O 17 Cl 2 . 2.4. Characterizations The crystal structure of the sample was analyzed by X-ray diffractometer (Bruker D8 Advance, Germany). Scanning electron microscopy (ZEISS Gemini SEM 300, Germany) was used to analyze its morphology and elemental composition. Transmission electron microscopy (TEM) and high-resolution TEM (HRTEM) were obtained on a transmission electron microscope (JEM-2100, Japan); UV/VIS/NIR diffuse reflectance test material with UV-Vis spectrophotometer (Shimadzu UV-3600, Japan) was used to test the light absorption performance of materials with BaSO 4 as the background and the scanning range was 200-800 nm. The catalyst was characterized by X-ray photoelectron spectroscopy (XPS) by X-ray photoelectron spectroscopy (Thermo Fisher Scientific K-Alpha, United States), and the chemical composition and valence state of the material were analyzed. Quantitative detection of tetracycline concentrations were measured by using a high-performance liquid chromatograph (Thermo DionexUltimate 3000, United States). Mineralization efficiency and total organic carbon (TOC) was determined by a total organic carbon analyzer (Multinz 3100, Germany). Mass-to-charge ratio of the degradation products was analyzed by high-resolution mass spectrometry (Thermo Scientific Q Exactive Orbitrap, United States). 2.5 Photocatalytic performance tests 10 mg of catalyst was dispersed in 20 mL of tetracycline hydrochloride solution at a concentration of 20 mg/L, mixed and stirred for 30 min at dark to achieve the adsorption-desorption equilibrium. Then, the solution was irradiated by 300 W xenon lamp (Jinyuan, Beijing, China) with a 420 nm cut-off filter. Meanwhile, 1 mL of the reaction solution was taken every 3 minutes with a syringe, filtered through a 0.22 μm filter, and tested by a high-performance liquid chromatography (HPLC). The parameters of the HPLC were the following: chromatographic grade methanol and 0.1 % chromatography grade formic acid solution were used as mobile phase, and the column was 5 μm 150 mm × 4.6 mm C18 column. The flow rate was 1 mL/min, the column temperature was 35 °C, the sample volume was 10 μL, and the detection wavelength was 355 nm, and the test was performed with a gradient elution procedure. The stability and reusability of the Bi 12 O 17 Cl 2 /AgI photocatalyst were tested by 5 cycles of photocatalytic degradation of TC. The Bi 12 O 17 Cl 2 /AgI photocatalyst used in each experiment was centrifuged, washed with deionized water and absolute ethanol alternately for 3 times, dried at 60 °C in the oven, and then cycled. Mineralization efficiency analysis was performed using a total organic carbon (TOC) analyzer. All tests were performed three times together. According to the standard curve y = 0.3435x - 1.0894, R² = 0.9999, Test data was converted to tetracycline relative concentration C (mg/L). The degradation efficiency of tetracycline can be calculated from equation (1): Degradation efficiency= (𝐶 0 - 𝐶 𝑡 ) /𝐶 0 × 100% (1) where C 0 is the initial concentration of tetracycline, and C t is the concentration of tetracycline at the time of photodegradation. Fig. 1 (a) XRD patterns of obtained Bi 12 O 17 Cl 2 samples with different pH values and (b) XRD patterns of the as-built composites and bare AgI. 2.6 Electrochemical tests By using an electrochemical workstation (CHI660E, Chenhua, China), the catalyst-coated FTO glass, platinum wire and Ag/AgCl (saturated KCl) electrodes were used as working electrodes, the reference electrodes and reference electrodes, respectively. Meanwhile, 0.1 M Na 2 SO 4 solution as the electrolyte, transient photocurrent response, electrochemical impedance spectroscopy (EIS) and Mott-Schottky were conducted to test the photoelectric properties of the composites. 2.7 Determination of active substances The key active substances for photocatalytic degradation of TC were identified through active substance capture experiment. Different quenching agents, such as Na 2 C 2 O 4 , tert-butanol (TBA), L-histidine (L-His), AgNO 3 and ascorbic acid (VC), were introduced into the photocatalytic system to determine effects of h + , ·OH, 1 O 2 , e - and ·O 2 - on the reaction process, respectively. 3. Results and discussion 3.1 Structures and morphologies of the Bi 12 O 17 Cl 2 /AgI heterojunctions The structure of the prepared photocatalyst was characterized by X-ray diffraction, and the crystal structure and phase composition of Bi 12 O 17 Cl 2 , AgI and B 12 OC/AgI heterojunctions were studied. As can be seen in Fig. 1a , When the pH value was equal to 4, the reactive synthesized material exhibited a BiOCl tetragonal structure (JCPDS No.82-0485). When the pH value was raised to 5, the characteristic peaks of the material at 24.10°, 30.18°, and 32.43° matched the (2 1 1), (4 0 5), and (10 1 1) planes of the Bi 12 O 15 Cl 6 orthorhombic crystal structure (JCPDS No. 70-0249). By further adjusting the pH to 6, the diffraction peaks are evident at 26.35°, 29.19° and 47.20°, corresponding to the (1 1 5), (1 1 7), and (2 2 0) crystal planes, respectively. All diffraction peaks can be traced back to the tetragonal phase of Bi 12 O 17 Cl 2 (JCPDS NO.37-0702), which indicates the successful synthesis of a pure Bi 12 O 17 Cl 2 crystal structure [33].These results suggest that an increase in the pH of the solution leads to a decrease in the Cl - content in the crystals. It is inferred that there is competition between OH - and Cl - in alkaline solutions, while the weak interlayer van der Waals force between Cl - in BiOCl makes it easy to replace or remove [34]. Thus, OH - replaces Cl - in the crystal lattice, destroying the stoichiometric layered structure while forming a non-stoichiometric product. The results showed that Bi-rich BixOyClz could be selectively prepared by adjusting the pH value of the reaction. Fig. 1b shows the crystal structure of 3D/0D B 12 OC/AgI nanocomposites with different mass ratios of pure AgI and different doping amounts. As shown in the figure, the diffraction peaks of the pure AgI sample are in good agreement with the structure of the AgI hexagonal crystal system (JCPDS NO.09-0399).The diffraction peaks of 22.31°, 23.70°, 39.20° and 46.30° can be well pointed to the (1 0 0), (0 0 2), (1 1 0) and (1 1 2) planes of the AgI hexagonal crystal system, respectively [35]. After the introduction of AgI, both AgI and Bi 12 O 17 Cl 2 peaks existed in the B 12 OC/AgI-15 composites. The results indicated that AgI and Bi 12 O 17 Cl 2 coexisted. Moreover, most of the characteristic peaks of AgI were included, which further indicated that AgI was Fig. 2 (a) SEM image of Bi 12 O 17 Cl 2 microfloral. (b) SEM image of AgI. (c) SEM image of B 12 OC/AgI-15 heterojunction. (d) TEM image of B 12 OC/AgI-15 heterojunction. (e) HRTEM image of B 12 OC/AgI-15 heterojunction. (f) EDS spectra of B 12 OC/AgI-15 heterojunction. (g) Mapping of B 12 OC/AgI-15 heterojunction. successfully grown on Bi 12 O 17 Cl 2 . In addition, according to the comparison of the XRD standard cards, no new diffraction peaks appeared in the composites compared to the original AgI and Bi 12 O 17 Cl 2 , indicating that the introduction of AgI did not change the crystalline phase of Bi 12 O 17 Cl 2 during the formation of B 12 OC/AgI-15. The XRD results fully demonstrated the successful synthesis of the Bi 12 O 17 Cl 2 /AgI photocatalyst. With the increasing of AgNO 3 addition, the peak intensities of (0 0 2) crystal plane of the hybrid composites increased, indicating that more and more AgI was generated. The morphology of Bi 12 O 17 Cl 2 , AgI, and B 12 OC/AgI-15 was studied by scanning electron microscopy, as shown in Fig. 2 . The bare Bi 12 O 17 Cl 2 sample presented a microfloral-like nanostructure composed of nanoplate ( Fig. 2a and Fig. S1 ), and the surface of Bi 12 O 17 Cl 2 was relatively smooth with rich vacancies derived from the calcination, which can increase the surface area [36]. As displayed in Fig. 2b , it was found that the AgI presented agglomerated zero-dimensional (0D) nanoparticles. Once forming the heterojunction, AgI nanoparticles were evenly dispersed on the surface of Bi 12 O 17 Cl 2 nanoplate, which effectively formed a compact heterojunction interface between AgI and Bi 12 O 17 Cl 2 ( Fig. 2c and Fig. S2 ). Meanwhile, the prepared B 12 OC/AgI-15 composite was further characterized by transmission electron microscopy (TEM), as shown in Fig. 2d . It was observed that many black and grey areas were attributed to the AgI NPs and B 12 OC, respectively, indicating that the nanosized AgI NPs were tightly embedded on the surface of Bi 12 O 17 Cl 2 , forming a well-defined microfloral-nanoparticle- (3D/0D) heterostructure, which was conducive to efficient separation and transportation of photogenerated charge carriers [37]. As displayed in Fig. 2e , the lattice fringes at the interface with a distance of 0.2793 nm and 0.3719 nm are derived from the (2 0 0) and (0 0 2) planes of the tetragonal Bi 12 O 17 Cl 2 and AgI, respectively, proving the successful synthesis of the Bi 12 O 17 Cl 2 /AgI heterojunction. In addition, the presence of Ag, I, Bi, Cl, and O elements was further confirmed by energy-dispersive x-ray (EDX) ( Fig. 2f ) and elemental mapping ( Fig. 2g ), which is consistent with the XRD results. The EDS results show the co-existence of Bi, Ag, Cl and I elements. The mass ratios of Bi, Ag, Cl and I were 81.52%, 0.26%, 3.19% and 2.44%, respectively. The element mapping Fig. 3 High-resolution XPS spectra of (a) all elements, (b)Ag 3d, (c)I 3d, (d)Bi 4f, (e)Cl 2p, and (f)O 1s of B 12 OC / AgI-15. of the B 12 OC/AgI-15 ( Fig. 2g ) further shows that these elements are evenly distributed in the Bi 12 O 17 Cl 2 /AgI composite. The detection results of XRD, HRTEM and EDX proved that AgI nanoparticles were successfully and evenly loaded on Bi 12 O 17 Cl 2 , and Bi 12 O 17 Cl 2 and AgI formed a 3D/0D heterojunction composite structure. Fig. 4 (a) Dark adsorption efficiency of B 12 OC/AgI-15 for TC and pure light degradation efficiency of TC. (b) Photocatalytic degradation of tetracycline by different samples. (c) Kinetic fitting diagram. (d) Mineralization efficiency over the B 12 OC/AgI-15 sample. The chemical bonding and surface element composition of the Bi 12 O 17 Cl 2 /AgI heterojunction were investigated by XPS, which confirmed the presence of Ag, I, Bi, Cl, C, and O elements in B 12 OC/AgI-15, as displayed in Fig. 3a. In Fig. 3b, it shows that there are two characteristic peaks in the Ag 3d spectrum at 368.55 eV (Ag 3d 5/2 ) and 374.60 eV (Ag 3d 3/2 ), indicating the presence of Ag + species rather than Ag 0 in the heterojunction [38]. For XPS spectra of I 3d in Fig. 3c , two characteristic peaks appeared at 619.20 eV and 632.60 eV were ascribed to the I 3d 5/2 and I 3d 3/2 , respectively [39]. As shown in Fig. 3d , in the high-resolution XPS spectrum of Bi 4f, the binding energies of two peaks at 159.61 eV and 164.93 eV, are attributed to Bi 4f 7/2 and Bi 4f 5/2 , respectively, indicating the presence of Bi 3+ ions in the heterojunction [40]. In the Cl 2p XPS spectra, the binding energies of Cl 2p 3/2 and Cl 2p 1/2 are situated at 198.61 eV and 200.24 eV, respectively, in Fig. 3e , indicating that the Cl element exists in the one valence state of Cl - [41]. Furthermore, the high-resolution XPS spectra of O 1s are shown in Fig. 3f , where the O 1s peak can be deconvoluted into two peaks at 530.49 eV and 531.54 eV attributed to the lattice oxygen and oxygen vacancies, respectively [42]. 3.2 Photocatalytic performances of these prepared heterojunctions Before photocatalytic degradation of tetracycline, firstly the adsorption equilibrium was achieved at dark adsorption for 30 minutes. In Fig. 4a , it was found that the adsorption of tetracycline was about 15% in the absence of light, indicating that the composite possessed a low adsorption capacity for tetracycline. Meanwhile, it was observed that the degradation rate of 20 mg/L tetracycline was only 3.5% with catalyst-free and light conditions. For the original Bi 12 O 17 Cl 2 and AgI, it was found that the photodegradation efficiency of tetracycline were 61.71% and 25.02%, respectively, after 15 min irradiation, as displayed in Fig. 4b . Furthermore, it was observed that the removal efficiencies of tetracycline over all of the B 12 OC/AgI samples exceeded 75% within 15 min. With the increase of AgI content, the photocatalytic activities of B 12 OC/AgI composites firstly increased and then decreased. Among them, the B 12 OC/AgI-15 had the highest photodegradation efficiency with a removal rate of 95.02% within 15 min. In order to better investigate the photocatalytic performance of the samples under visible light irradiation, the first-order kinetic reaction was used to fit the results [43]. -ln (C t /C 0 ) =kt (2) where C 0 is the concentration of the pollutant solution after reaching the dark Fig. 5 Photocatalytic performances of B 12 OC/AgI-15 heterojunction at different initial pH values (a), catalyst dosages (b) and TC concentrations (c). (d) active radical quenching experiment. adsorption equilibrium, and k is the degradation rate constant. The kinetic fit diagram was obtained and shown in Fig. 4c , the corresponding k of B 12 OC/AgI-15 to TC is 0.152 min -1 , which was 4.30 and 9.63 times higher than Bi 12 O 17 Cl 2 and AgI. The results demonstrated that the introduction of AgI was beneficial to promote the transfer of photoexcitation charge and inhibit the recombination of photogenerated electron-hole pairs, thereby increasing the photocatalytic performance. However, excessive deposition of AgI NPs on the surface of Bi 12 O 17 Cl 2 may reduce the number of exposed active centers and suppress the transfer of photogenerated carriers, which is not conducive to the further improvement of photodegradation activity [44]. Furthermore, the mineralization rate of TC under visible light irradiation was evaluated by detecting the change of total organic carbon (TOC). In Fig. 4d, the results of TOC presented that the mineralization efficiency of TC was positively correlated with its degradation rate. Under visible light irradiation, the B 12 OC/AgI-15 exhibited 42% of TC mineralization, which indicates that the heterojunction can efficiently mineralize the organic TC to CO 2 and H 2 O. Besides, the optimized B 12 OC/AgI-15 was selected as the representative catalyst to systematically investigate effects of important factors on the photodegradation of tetracycline, such as catalyst dosage, solution pH, and cycling. The photodegradation activities of B 12 OC/AgI-15 against tetracycline at different pH values from 3.0 to 11.0 were studied. As shown in Fig. 5a , it was found that, in the B 12 OC /AgI-15 system, the acidic environment presented an inhibitory effect on the degradation of TC, in contrast, the neutral and alkaline environment is conducive to the photocatalytic degradation of TC, which can achieve 90% within 15 min. It is speculated that the acid-base center of the composite may be destroyed under acidic conditions, affecting the structural stability, thereby reducing the photocatalytic degradation activity [45]. As shown in Fig. 5b , when the dosage of B 12 OC/AgI-15 increased from 0.25 g/L to 0.5 g/L, the degradation rate of TC increased rapidly from 62.9% to 95.3% within 15 min, indicating that the appropriate increase in the dosage of catalyst was conducive to the degradation of TC, because B 12 OC/AgI-15 had abundant reaction sites. In contrast, when the dosage of B 12 OC/AgI-15 was further increased from 0.5 g/L to 0.75 g/L or even 1.00 g/L, the degradation efficiency was not improved, which may be due to the fact that high concentration will increase light scattering, reduce the light transmittance of the solution, and limit the further improvement of photocatalytic performance. The degradation effect of the catalyst on different concentrations of TC was tested as displayed in Fig. 5c , after 15 minutes of illumination, the photocatalytic degradation efficiencies of TC with different concentrations were 98.2%, 95.0%, Fig. 6 (a) cycle experiment of photocatalytic degradation of tetracycline, (b) XRD comparison of materials before and after cycling, and (c, d, e, f) comparison of XPS between B 12 OC/AgI-15 before and after recycling tests. 59.7%, and 50.3%. As the TC concentration increases, the degradation efficiency decreases, which mainly were attributed to the finite number of active site on the surface of the heterojunction. To better elucidate the reaction mechanism, radical quenching experiments were performed to reveal active radicals of photodegrading TC over B 12 OC/AgI-15 heterojunction under visible light illumination ( Fig. 5d ). Sodium oxalate (Na 2 C 2 O 4 ), tert-butanol (TBA), L-histidine (L-His), AgNO 3 , and ascorbic acid (VC) were used as quenchers to scavenge h + , ·OH, 1 O 2 , e - , and ·O 2 - [46]. In the presence of VC and Na 2 C 2 O 4 , the degradation efficiency of B 12 OC/AgI-15 decreased sharply from 95.02% to 16.98% and 66.47%, respectively, indicating that the ·O 2 - and h + play a crucial role in the degradation of TC under visible light irradiation. Since the photostability and durability of the photocatalyst are very important for its practical application, the photostability of B 12 OC /AgI-15 under simulated sunlight were investigated. As shown in Fig. 6a , after 4 cycles, the degradation rate of TC over the B 12 OC/AgI-15 was still over 80%. Meanwhile, XRD patterns of the used B 12 OC/AgI-15 heterojunction after cycling ( Fig. 6b ) were performed. Comparing the cycled B 12 OC/AgI-15 XRD with the standard card, we found no characteristic peaks of Ag after catalysis, which indicated that the crystal structure of the used B 12 OC/AgI-15 did not change significantly in comparison with the fresh sample, which demonstrated thatB 12 OC/AgI-15 possessed a largely stable structure. The B 12 OC/AgI-15 heterojunction before and after cycling was further tested by XPS, and the comparison results were as shown in Fig 6c -f. The Bi 4f, Cl 2p, Ag 3d and I3d spectra of the B 12 OC/AgI-15 heterojunction basically did not change before and after cycling, and there was no characteristic peak of Ag elemental in the XPS spectra of Ag 3d. Conclusions can be drawn from the results of XPS and XRD analysis of recycled materials. The combination of Bi 12 O 17 Cl 2 and AgI can effectively prevent the coupling of photoelectrons with interstitial Ag + to form metal Ag, thereby improving the light corrosion resistance of B 12 OC/AgI-15 heterojunction, effectively improving the recycling performance of heterojunction and ensuring structural stability. 3.3 Photoelectrochemical properties of the B 12 OC/AgI heterojunctions Ultraviolet-visible diffuse reflectance spectroscopy was used to study the optical Fig. 7 (a) UV−vis diffuse reflectance spectra of Bi 12 O 17 Cl 2 , AgI and B 12 OC/AgI-15; (b) Tauc plots of Bi 12 O 17 Cl 2 , AgI and B 12 OC/AgI-15. (c) instantaneous time-response current and (d) EIS Nyquist plots of Bi 12 O 17 Cl 2 , AgI, and B 12 OC/AgI-15. properties of the Bi 12 O 17 Cl 2 , AgI, and B 12 OC/AgI-15 photocatalyst, as shown in Fig. 7a . It was observed that the absorption edges of the bare Bi 12 O 17 Cl 2 and AgI are situated at about 380 nm and 460 nm, respectively. Meanwhile, the absorption edge of B 12 OC/AgI-1 was located in the middle of Bi 12 O 17 Cl 2 and AgI, which indicated that the introduction of AgI can effectively expand the photo absorption range and reduce the band gap, thereby improving the photocatalytic activity. The band gap energies can be calculated by equation (3): ( α hν) 1/n =A (hν - E g ) (3) where α is the optical absorption coefficient, ν is the frequency of the light, h is the Planck constant, E g is the bandgap energy, and n depends on the type of optical transition of the semiconductor. n=1/2 when the semiconductor material is a direct Fig. 8 (a) Mott-Schottky curve of Bi 12 O 17 Cl 2 (b)Mott-Schottky curve of AgI. bandgap and n=2 when the semiconductor material is an indirect bandgap. For both Bi 12 O 17 Cl 2 and AgI, n is 2. The Tauc plot was plotted and displayed in Fig. 7b , where the E g values of Bi 12 O 17 Cl 2 and AgI were calculated to be 2.92 eV and 2.78 eV, respectively, and the E g values of B 12 OC/AgI-15 was equal to 2.80 eV, which demonstrated that the introduction of AgI NPs decreased the bandgap energy of heterojunction. In order to measure the photogenerated charge carrier separation and transfer efficiency of these samples, the instantaneous time-response current and electrochemical impedance (EIS) were conducted. In general, a higher photocurrent means a lower recombination rate of the photo-induced e - −h + pairs [47]. As displayed in Fig. 7c , it is clearly observed that the transient photocurrent density of B 12 OC/AgI-15 is higher than that of AgI and Bi 12 O 17 Cl 2 , indicating a higher charge separation dynamic, which inferred that the photogenerated carriers over the constructed heterojunction have higher separation and migration efficiency. In addition, in Fig. 7d , the EIS showed a faster charge transfer kinetic for the B 12 OC/AgI-15 heterojunction because the arc radius of B 12 OC/AgI-15 heterojunction was the smallest among the arc radii of the pristine Bi 12 O 17 Cl 2 and AgI, B 12 OC/AgI-15 heterojunctions [48]. 3.4 Photocatalytic mechanism over the B 12 OC/AgI heterojunctions Fig. 9 Schematic diagram of band structure of the pristine Bi 12 O 17 Cl 2 and AgI before and after formation of heterojunction. In order to explore the accurate band structure of Bi 12 O 17 Cl 2 , AgI, B 12 OC/AgI-15, the Mott-Schottky curves are shown in Fig. 8a and b . It was clearly observed that the Mott-Schottky slopes of AgI and Bi 12 O 17 Cl 2 are positive, indicating that both of the single photocatalyst are an n-type semiconductor [49]. The flat band potentials ( E fb ) of Bi 12 O 17 Cl 2 and AgI are about -0.84 V and -0.63 V vs. Ag/AgCl. At the same time, according to the equation, E NHE = E Ag/AgCl + 0.197, the E fb of Bi 12 O 17 Cl 2 and AgI are -0.64 V and -0.43 V vs. NHE [50]. In general, the E CB of n-type semiconductors is about 0.1 V more negative than that of E fb [51]. Accordingly, the E CB of Bi 12 O 17 Cl 2 and AgI are -0.74 and -0.53 V vs. NHE with the assistance of the Nernst equation, Consequently, the E VB of Bi 12 O 17 Cl 2 and AgI are 2.18 V and 2.25 V vs . NHE [52]. Based on the above characterizations, a possible photocatalytic mechanism is proposed and displayed in Fig. 9 . From the perspective of band structure, the CB position of pure AgI and Bi 12 O 17 Cl 2 are more negative than the potential of ·O 2 - generation (-0.33 eV vs. NHE), where the photogenerated electrons reduce the O 2 to ·O 2 - . The VB of Bi 12 OC/AgI was lower than the potential of ·OH (+2.38 eV vs. Fig. 10 (a) High-resolution mass spectra of TC degradation products at 15 min, (b) Illustrator of the proposed possible degradation pathways of TC. NHE) [53]. Therefore, Bi 12 OC/AgI cannot directly react to produce ·OH through electron transport. The ·OH mainly comes from the secondary decomposition of ·O 2 - . This is consistent with the results of the free radical quenching experiment, h + and ·O 2 - are the main active substances, and ·OH is the secondary active substances. Therefore, based on the band structure of AgI and Bi 12 O 17 Cl 2 , it was speculated that the AgI and Bi 12 O 17 Cl 2 were combined to form a type II heterojunction. The path of photocatalytic degradation of TC over Bi 12 OC/AgI was as follows: under visible light irradiation, both of AgI and Bi 12 O 17 Cl 2 can be excited to produce holes and electrons, and then the photoinduced electrons located at CB of the Bi 12 O 17 Cl 2 were transferred to CB of the AgI which can combine with molecular oxygen to form oxidation O 2 - [54]. Correspondingly, the holes on the VB of AgI were transferred to the VB of Bi 12 O 17 Cl 2 , and the enriched holes at the VB of Bi 12 O 17 Cl 2 can directly react with pollutants to convert organic pollutants into small molecules. In addition, the interaction band structure of AgI and Bi 12 O 17 Cl 2 causes the photogenerated holes to transfer to the VB of Bi 12 O 17 Cl 2 , and the photogenerated electrons generated by AgI are involved in the reaction of O 2 to ·O 2 - . This avoids the reduction of the unstable excited state AgI to Ag by the recombination of photogenerated carriers, and improves the stability of AgI under visible light irradiation [55]. The peroxide radical generated by Bi 12 OC/AgI significantly improved the photocatalytic degradation performance. Furthermore, HPLC-MS was used to detect the intermediate products of antibiotic during the photodegradation process, which is helpful to understand and propose the degradation pathway of tetracycline hydrochloride. Mass spectra of TC after degradation at 15min were displayed in Fig. 10a. It was found that after degradation, the m/z values of 406, 362, 318, 274, and 144 were detected, among which the m/z peak of 445 was basically undetectable, proving that TC was almost completely degraded. As the photocatalytic time increased, some new peaks with smaller m/z values appeared. The results showed that after 15 min, the TC molecule was converted into a small organic product. From the mass spectrometry at 15 min, almost no macromolecular substances were found. Due to the high electron density of the double-bonded, phenolic, and amine functional groups, these three functional groups are more susceptible to attack by free radicals [56]. Combined with the previous studies, the transformation products of TC in the degradation process are more complex, including dehydration, hydroxylation, demethylation, decarboxylation, demethylation oxidation and other products [57]. Based on mass spectrometry analysis, we speculated three possible transformation pathways for TC photodegradation, as displayed in Fig. 10b . In pathway 1 and 2, the dimethylamine group of TC molecule (m/z = 445) was attacked by h + or ·O 2 - and converted to m/z = 362. After further demethylation, the intermediates m/z = 318 and m/z = 274 were produced, respectively. After that, the products at m/z = 230 and m/z = 214 were obtained by ring-opening reaction and dehydration. Besides, two substances at m/z = 186 and m/z = 144 were formed through a removal reaction of phenyl group and then m/z = 102 was obtained via further ring-opening reaction. Finally, these small molecules may be further degraded to CO 2 and H 2 O, suggesting that TC was eventually mineralized. In addition, for pathway III, TC was attacked by active radicals and converted to m/z = 406 through a dehydration reaction. After that, the phenyl group was removed to obtain m/z = 274, then the continuous ring-opening reaction was proceeded to generate m/z = 124 and m/z = 94, respectively. Finally, the small molecule organic matter was mineralized into CO 2 and H 2 O. 4. Conclusions In summary, a novel 3D/0D Bi 12 O 17 Cl 2 /AgI heterojunctions were successfully prepared by dispersing AgI QDs on the surface of three-dimensional Bi 12 O 17 Cl 2 . The composite exhibited excellent photocatalytic performance in photodegraded tetracycline. The B 12 OC/AgI-15 presented the best degradation performance, and the degradation efficiency of TC within 15 min was 95.02%. Enhanced photocatalytic activity stems from the formation of type II heterojunction, which can efficiently improve charge separation and retain more electrons and holes. The photodegradation removal of tetracycline over the B 12 OC/AgI was still greater than 80% after five repeated usages, indicating that the composite possessed excellent stability and reusability performance. This study can provide a path to the construction of Bi-based heterojunctions with unique structures and the development of high-performance photodegradation catalysts. Conflicts of interest There are no conflicts to declare. 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Keywords bi12o17cl2 oxygen vacancies photocatalysis silver iodide tetracycline hydrochloride type ii heterojunction Authors Affiliations Zhaoyang Yan Wuhan Institute of Technology View all articles by this author Jun Ke 0000-0002-3734-5729 [email protected] Wuhan Institute of Technology View all articles by this author Yixuan Hu Wuhan Institute of Technology View all articles by this author Lulu Zhao Wuhan Institute of Technology View all articles by this author Jie Yan Wuhan Institute of Technology View all articles by this author Ranxing Wang Wuhan Institute of Technology View all articles by this author Metrics & Citations Metrics Article Usage 168 views 89 downloads .FvxKWukQNSOunydq8rnd { width: 100px; } Citations Download citation Zhaoyang Yan, Jun Ke, Yixuan Hu, et al. Silver iodide decorated Bi12O17Cl2 heterojunction with enriched oxygen vacancies toward efficiently enhanced mineralization of antibiotics. Authorea . 02 January 2025. 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