Contribution of multi-metal oxides based on SrMnO 3 for the enhanced formation of Ov on chlorobenzene degradation: performance and mechanism

Contribution of multi-metal oxides based on SrMnO 3 for the enhanced formation of Ov on chlorobenzene degradation: performance and mechanism | 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 Contribution of multi-metal oxides based on SrMnO 3 for the enhanced formation of Ov on chlorobenzene degradation: performance and mechanism Peng Yu, Jing Shi, Hangjiang Wan, Zijian Tang, Kangyu Yuan, Xi Li, and 3 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-5995427/v1 This work is licensed under a CC BY 4.0 License Status: Under Review Version 1 posted 7 You are reading this latest preprint version Abstract The degradation of chlorinated volatile organic compounds (CVOCs) using conventional chalcogenide catalyst is often hindered by the accumulation of chlorine species and the loss of active sites. Although SrMnO 3 improves the degradation efficiency of pollutants by inhibiting chlorine species accumulation due to its high thermal stability and oxygen mobility, chlorine toxicity remains a concern. In this work, a multi-metal oxide based on SrMnO 3 was synthesized by hydrothermal method, with Ce introduced to increase surface deficiency, thereby exposing more active sites. The influences of catalyst dosage, relative humidity, pollutant concentration and airspeed on chlorobenzene (CB) degradation were systematically investigated, with the highest CB removal efficiency achieved by T 90 = 247 ℃, T 95 = 269 ℃, mineralization rate = 71%. The catalytic mechanism was investigated with systematical characterizations and the possible degradation pathways of CB were also inferred with GC-MS. This study would provide new insights and ideas for the design and synthesis of chalcogenide-based multi-metal oxide catalyst. Strontium manganate Ce doping Multi-metal oxide Catalytic combustion Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 1 INTRODUCTION Volatile organic compounds (VOCs) are major precursors of O 3 and PM 2.5 , emitted in large quantities that pose a serious threat to human health and the environment (He et al., 2019 ; Xiao et al., 2022 ). As a significant subclass of VOCs, chlorinated volatile organic compounds (CVOCs), are emitted through volatilization and leakage during industrial, agricultural and pharmaceutical production processes. These pollutants are often difficult to biodegrade and some are “carcinogenic, mutagenic and teratogenic” to humans. Typically, catalytic combustion technology is commonly used for CVOCs treatment due to its wide application range, low oxidation temperature and low energy consumption. However, the chlorosis of catalysts, caused by chlorine-containing species generates during CVOCs degradation, significantly limits the further application of this technology. Therefore, it is crucial to develop high-performance catalysts for the catalytic combustion of CVOCs to minimize chlorosis and the formation of secondary toxic by-products. Perovskites consist of isolated metal halide octahedral anions surrounded by organic or inorganic cations, with excitons strongly confined to each octahedron (Sun et al., 2021 ). Crystal defects (e.g., vacancies) in perovskite provide channels for ion migration during the catalytic combustion process (Zhou et al., 2019 ). These defects promote the migration and reaction of oxygen ions, enhancing oxygen mobility and facilitating the efficient degradation of CVOCs (Choudhary et al., 2002 ; Gélin and Primet, 2002 ; Royer et al., 2014 ). However, the performance of perovskite for pollutant degradation mainly depends on the rational design and modulation of its structure-function relationship and surface properties (Blasin-Aubé et al., 2003 ). For a typical perovskite catalyst, the A-site cation only stabilizes the structure with no catalysis process occurring, while A/B-site doping of perovskites would alter the physicochemical property and the performance of the catalyst (Zhu and Thomas, 2009 ; Onrubia-Calvo et al., 2017 ; Yang and Teng, 2018). It has been reported that the incorporation of Cs + in δ-CsPbI 3 provides alternative phase transition pathways to the perovskite phase and creates sparse nucleation centers for further crystal growth (Qin et al., 2020 ). Additionally, doping of A-site cations would promote the valence transformation of B-site element. Studies using techniques such as XRD, BET, XPS and H 2 -TPR have revealed changes in the oxidation states of the B-site cation Mn, as well as alterations in the overall redox properties of perovskite due to A-site substitution (Rezlescu et al., 2014 ; Doggali et al., 2015 ). La- or Sr-based perovskites containing Co, Fe, or Mn as the M cation exhibited great performance in catalytic combustion, while the manganese-based perovskites exhibited high performance and cost-effectiveness (Arai et al., 1986 ). Manganese-based perovskites are cost-effective, exhibit high catalytic performance and effectively promote catalytic combustion reactions (Rezlescu et al., 2014 ; Eom et al., 2018 ). The rare-earth element Ce has garnered increasing attention in catalysis due to its unique electron arrangement (Raabe et al., 2012 ; Qian et al., 2020b ). The introduction of Ce ions alters the charge distribution of the catalyst, compensates for charge imbalances, induces the formation of oxygen vacancies (O V s) and promotes the valence cycling of B-site element. Optimal rare earth doping stabilizes the lattice structure and reduces the formation energy of O V s, as well as the energy for oxygen adsorption and dissociation, thereby enhancing catalytic performance (Zhang et al., 2020a ). When the molar ratio of Ce in (La + Ce) exceeds 0.4, Ce readily incorporates into the LaFeO 3 structure, facilitating the catalytic combustion reaction (Ovejero et al., 2012 ). Sun et al. found that, the increased content of Ce facilitated the formation of O V s in La 1 − x Ce x FeO 3−δ with oxygen adsorbing on O V s to form reactive oxygen species. (Sun et al., 2019 ). In addition, cerium oxide would also introduce additional O V s into the catalyst. Yuan et al. found that CeO 2 , generated after Ce doping, would store or release O 2 through Ce 4+ /Ce 3+ redox pairs (Yuan et al., 2012 ; Nasirian et al., 2017 ). Besides, the O V s on the CeO 2 surface would also enhance O 2 adsorption. Qian et al. found that the introduction of Ce into the A cation of LaCoO 3 enhanced the catalytic performance in oxygen precipitation and reduction reactions (OER/ORR) (Qian et al., 2020a ), which also promoted a higher number of O V s and Co 3+ /Co 2+ and Ce 4+ /Ce 3+ redox pairs to enhance the performance of CB combustion (Zhu and Thomas, 2009 ). In this study, a SrMnO 3 -based multi-metal oxide catalyst was designed and synthesized, with Ce incorporated to increase the defectivity and stability of catalyst to ensure catalytic performance even after the occupation of active sites by chlorine species. Various characterizations were performed to investigate the morphological structure and chemical composition of the catalysts. Influences of pollutant concentration, catalyst dosing, airflow speed and relative humidity were systematically investigated. The catalytic degradation mechanism was inferred by identifying the major substances generated in the degradation process. Possible degradation pathways and the environmental toxicity of intermediates were further assessed through intermediate product analysis (GC-MS). 2 METHODS 2.1 Chemicals and materials All the chemicals and reagents in this work were analytical-grade or high-performance gas chromatography (HPGC) grade reagents without any purification. Strontium acetate hemihydrate (Sr(CH 3 CO 2 ) 2 ·0.5 H 2 O), cerium nitrate hexahydrate (Ce(NO 3)3 ·6H 2 O), manganese acetate tetrahydrate (Mn(CH 3 COO) 2 ·4 H 2 O), KOH were all purchased from Sinopharm Chemical Reagents Co., Ltd. (Nanjing, China). CB was provided by Aladdin Chemical Co., Ltd (Shanghai, China). Deionized water used throughout all experiments were generated by water purification instrument (GWB-UP, Persee, China). The tap water was supplied by Nanjing Chemical Industrial Park Water Industry Co., Ltd. (Nanjing, China). 2.2 Preparation of catalysts A series of Sr-Ce-Mn-Ox catalysts were synthesized using a hydrothermal method (Fig. 2 (a)). Strontium acetate hemihydrate, cerium nitrate hexahydrate and manganese acetate tetrahydrate were weighed in specific molar ratios and sequentially dissolved in purified water (20 mL). KOH solution (5 M) was added dropwise to the homogeneous solution and the pH was adjusted to 13.5 ± 0.5. The solution was then transferred to a 100 mL high-pressure reactor and reacted at 180 ℃ for 16 hours. Finally, the resulting materials were washed with purified water to neutrality and dried overnight. The materials were labeled as SCM-0, SCM-1, SCM-2, SCM-3, SCM-4 and SCM-5 in a specific order (Table S1 ). 2.3 Characterization method Morphology investigation was recorded by scanning electron microscope (SEM, Supra 55, Carl Zeiss, Germany). Transmission electron microscope (TEM) and high-resolution TEM (HRTEM) were performed on a JEM-200CX instrument (JEOL, Japan) with energy disperse spectroscopy (EDS) applied to analysis the elemental composition and distribution. X-ray diffraction (XRD) analysis was carried out on a DMAX-2400 diffractometer (Rigaku, Japan) at 40 kV and 40 mA with Cu Kα radiation (λ = 0.15406 Å). The elemental composition and oxidation states were obtained by a Nexsa X-ray photoelectron spectroscopy (XPS, Thermo Fisher, USA) and all the binding energies were calibrated with the peak of 284.8 eV on the C 1s spectrum with detailed information presented in Text S1 of supporting information. H 2 -temperature programmed reduction (H 2 -TPR), O 2 -temperature programmed desorption (O 2 -TPD) and NH 3 -temperature programmed desorption (NH 3 -TPD) were performed on a Temperature programmed chemical adsorption analyzer (Micromeritics AutoChem II 2920 instrument, America). 2.4 Catalytic evaluation For the catalytic performance test, CB was selected as the characteristic pollutant. A mixture of 100 mg of catalyst and 800 mg of quartz sand was placed in a quartz tube (6 mm in diameter), sealed with quartz cotton at both ends and heated in a tube furnace. The furnace temperature could be programmatically controlled and the reaction temperature was monitored (Fig. 1 ). The reaction temperature ranged from 30 to 300 ℃, with temperature points at 30 ℃ and 60 ℃, and a 50 ℃ gradient from 100 ℃ to 300 ℃ every 50 minutes. Performance data were recorded once the reaction reached a steady state (after stabilizing for 40 minutes) for CB gas concentration. The inlet gas concentration and humidity were controlled using a micro syringe pump and gas generator. The CB concentration was maintained at approximately 4000 mg m –3 , with O 2 (21 vol.%) and N 2 as the equilibrium gases. The total gas flow rate was 100 mL min –1 and the airflow rate was 70.15 g airflow g cat –1 h –1 . A methane conversion furnace was used to convert the outlet gas into CO 2 and the mineralization rate of the pollutants was then calculated. 3 RESULTS AND DISCUSSION 3.1 Characterization The X-ray diffraction (XRD) patterns of the synthesized catalysts were exhibited in Fig. 2 (a). The phase compositions of the catalysts with different metal doping ratios were similar and the materials primarily consisted of SrMnO 3 , CeO 2 , SrO and MnO 2 . The XRD peaks of the samples in the 2θ range from 5° to 80° corresponded well to those of the SrMnO 3 standard card (JCPDS No. 00-025-0900), indicating that the resulting catalyst conforms to the perovskite crystal structure. The sample's crystal structure was orthorhombic. Characteristic diffraction peaks of CeO 2 and MnO 2 appeared at 2θ = 28.56°, 33.08°, 47.49°, 56.33° and 2θ = 21.82°, 35.17°, respectively. Thus, it could be concluded that the chalcogenide-type catalysts were successfully prepared, with SrO, MnO 2 , Mn 3 O 4 and CeO 2 being produced during synthesis, consistent with the TEM characterization results. Absorption bands for Mn-O stretching vibrations in the catalyst series were observed at 633, 529 and 420 cm –1 (Fig. 2 (b)). The Ce-O vibrational bands likely overlapped with those at 529 cm –1 and did not appear separately. Bands at 569 and 689 cm –1 were consistent with the Ce-O stretching vibrational mode, resulting from the partial reduction of Ce 4+ to Ce 3+ . The stretching vibrations of Ce-O-Ce bonds were observed at 551 cm –1 . Figure 3 showed the microscopic morphology of the samples. After doping with Ce, the surface morphology changed from stacked clusters in SCM-0 to smaller, more dispersed clusters in SCM-2. A comparison of Fig. 3 (c) and Fig. 3 (g) revealed a decrease in particle size, accompanied by an increase in specific surface area (37.46 m 2 g –1 for SCM-0 to 76.76 m 2 g –1 for SCM-2). The N 2 adsorption-desorption isotherms and pore size distributions (Fig. S1 ), along with the surface area and pore structure results (Table S2), were consistent with the SEM image data. The results indicated that the changes in morphology and surface area of the Ce metal-doped materials were due to the CeO 2 formed during synthesis. The presence of Ce 3+ and Ce 4+ exacerbated lattice distortion (Zhang et al., 2020b ; Jiang et al., 2023 ), which significantly increased the surface area. This suggested that Ce introduction into the chalcogenide lattice raises the concentration of O V s (Ansari et al., 2020 ). Generally, a high specific surface area increased the number of active surface sites, making it easier for reactant molecules to adsorb onto the catalyst surface. This facilitated deeper oxidation and improved the catalyst’s performance (Ding et al., 2016 ; Li et al., 2022 ; Liu et al., 2022 ). The specific substances in SCM-0 and SCM-2 were characterized by TEM-EDS and the results were presented below. Figure 3 (d, e, h, i) clearly showed that the four substances, SrMnO 3 , MnO 2 , Mn 3 O 4 and SrO, were present in both samples. The key difference was that SCM-2 contained more CeO 2 , confirming that CeO 2 was generated during the synthesis of the Ce-metal doped sample SCM-2. XPS spectra provided precise information about the surface elemental composition, metal oxidation states and adsorbed species of solid materials. Figure 4 presented the Sr 3d, Ce 3d, Mn 2p and O1s XPS spectra for both samples. Mn 3+ and Mn 4+ species were present on the surface of both samples, along with surface lattice oxygen (O latt ) and adsorbed oxygen (O ads , e.g., O 2– , O 2 2– and O – ). The atomic ratios of Mn 4+ /Mn 3+ and O latt /O ads on the surface significantly affected the catalytic oxidation performance of manganates for VOCs (Boningari et al., 2015 ; Chen et al., 2019 ). Figure 5 (e) showed the Mn 2p 3/2 XPS spectra of SCM-2 samples at BE = 641.4, 642.6 and 643.9 eV, which could be decomposed into three components corresponding to surface Mn 2+ , Mn 4+ and Mn 3+ species, respectively (Alifanti et al., 2003 ; Li et al., 2019a ; Zhu et al., 2020 ). SCM-2 exhibited a lower Mn 4+ /Mn 3+ molar ratio on the surface compared to SCM-0, likely due to the conversion of Mn 4+ to Mn 3+ during the catalytic oxidation of CB. A specific Mn 4+ /Mn 3+ molar ratio correlated with lattice defects, promoting the redox properties of chalcogenides and enhancing catalytic performance (Di Benedetto et al., 2022 ). The peaks at 882.6 eV and 901.2 eV corresponded to Ce 3+ , associated with the Ce 3d 5/2 and Ce 3d 3/2 states, respectively. The peak at 898.5 eV corresponded to Ce 2+ and the peaks at 883.8, 907.7 and 917.0 eV correspond to Ce 4+ (Wang et al., 2014 ; Meng et al., 2018 ). The results indicated that Ce 2+ , Ce 3+ and Ce 4+ coexisted on the catalyst surface. The formation of Ce 3+ promoted the generation of O V s, with higher Ce 3+ concentrations leading to a greater O V s concentration on the catalyst surface (Acharya et al., 2020 ). Performance tests showed that the Ce-doped SCM-2 samples exhibited the highest performance, suggesting that Ce 3+ in the catalyst positively contributes to the reaction catalysis. The O1s spectra for each sample at BE = 529.9, 531.6 and 533.8 eV could be decomposed into three components: O latt , O ads (She et al., 2018 ; Jiang et al., 2019 ) and surface carbonate (CO 3 2– ). O latt primarily served as the oxidizing species, while O ads replenished consumed O latt . CeO 2 , due to its strong oxygen storage capacity, had a higher O latt content than other catalysts (Table S2), resulting in the best CB oxidation performance. Thermodynamically, the C-Cl bond in CB had a lower bond energy, making it easier to break. CB was typically adsorbed and dissociated on surface active sites through nucleophilic attack on the C-Cl bond. The adsorbed material subsequently reacted with reactive oxygen species to form CO 2 and H 2 O. Simultaneously, the adsorbed dissociated Cl- was oxidized to Cl 2 by surface-active oxygen via the Deacon reaction (2 HCl + O 2 → Cl 2 + H 2 O). Finally, the consumed oxygen was replenished by gas-phase oxygen adsorbed onto the O V s (Biesinger et al., 2011 ; Lv et al., 2022 ). Therefore, O latt played a fundamental role and the catalytic performance of SCM-2 samples in CB oxidation improved with increasing surface-active oxygen concentration, particularly O latt . The redox capacity of the catalyst was measured by H 2 -TPR. Figure analysis showed that the fitting peaks of SCM-2 shift to a lower temperature compared to SCM-0, indicating the doped Ce enhanced the redox capacity of Mn 4+ /Mn 3+ and created a new Ce 4+ /Ce 3+ redox pair (Zhu et al., 2017 ). The reduction peaks in SCM-0 at 308 ℃ and 345 ℃ were primarily attributed to the valence reduction of Mn 4+ to Mn 3+ . The reduction peak at 458 ℃ corresponded to the reduction of Mn 3+ to Mn 2+ . In SCM-2, the valence reduction peak of Mn 4+ to Mn 3+ occurred at 277 ℃, 31 ℃ lower than in SCM-0. This shift indicated that Ce doping accelerates the Mn 4+ /Mn 3+ reduction process, mainly due to the introduction of Ce 4+ , which increased O V s concentration (Acosta Perez et al., 2023 ). This promoted the electron transfer, highlighting the role of Ce doping in enhancing the redox properties of the samples (Royer and Duprez, 2011 ; Li et al., 2019b ). SCM-2 exhibited better low-temperature reduction performance, with earlier reduction peaks, higher H 2 consumption and significantly improved catalytic performance for CB. From the Fig. 4 (e), it can be seen that the SCM-0 material has two sub-peaks, the reduction peak located at 32.15 min is attributed to the reduction of Mn 4+ to Mn 3+ and the peak at 43.31 min is attributed to the reduction of Mn 3+ to Mn 2+ and the integrals were carried out to obtain the consumptions of H 2 as 3.16 mmol g –1 and 2.65 mmol g –1 , respectively. Similarly, the two peaks of the modified SCM-2 material appeared at 23.92 min and 33.91 min, respectively (8.23 min and 9.40 min earlier compared to SCM-0) and were analysed to give H 2 consumption of 1.54 mmol g –1 and 1.64 mmol g –1 . The reduction peaks at lower temperatures are attributed to the reduction of Mn 4+ to Mn 3+ , while the reduction peaks at higher temperatures are attributed to the reduction of Mn 3+ to Mn 2+ . The area ratio at both temperatures is 0.84 for the SCM-0 material and 1.06 for the SCM-2 material, suggesting that more Mn 3+ is reduced to Mn 2+ , which is consistent with the data on the increase in Mn 3+ content in XPS. Figure 4 (f) shows NH 3 -TPD profiles of SCM-0 and SCM-2 catalysts. Both the catalysts exhibited a broad multiple peak which could be separated into two components, corresponding to weak and strong acid sites, in the temperature ranges of 100–200 ℃ and > 300℃. The NH 3 desorption at the weak and strong acid peaks of SCM-0 material was calculated to be 0.19 mmol g –1 and 0.01 mmol g –1 , respectively, and similarly the NH 3 desorption at the weak and strong acid peaks of SCM-2 material was calculated to be 0.36 mmol g –1 and 0.07 mmol g –1 , respectively. The increase of NH 3 desorption at the weak and strong acid peaks of the modified SCM-2 material indicates that the material has better resistance to carbon accumulation and sintering and has a high degree of carbon resistance. 0.07 mmol g –1 . The increased NH 3 desorption at the weak acid peak of the modified SCM-2 material indicates that the material has better resistance to carbon accumulation and sintering and has high selectivity to convert most of the CB into CO 2 and HCl, which inhibits the generation of by-products. Meanwhile, the increase of NH 3 desorption at the position of the strong acid peak indicates that the activity of the material is significantly improved and the reaction rate is accelerated. 3.2 Catalytic performance With no catalyst, no significant CB conversion improvement was observed below 300 ℃, indicating no homogeneous reaction occurred in the condition of CB concentration maintained at approximately 4000 mg m –3 , with O 2 (21 vol.%) and N 2 as the equilibrium gases. The total gas flow rate was 100 mL min –1 and the airflow rate was 70.15 g airflow g cat –1 h –1 ). T 50 and T 90 corresponded to the reaction temperatures for CB conversions of 50% and 90%, respectively. For SCM-0 and SCM-2, T 50 was 194 and 171 ℃, T 90 was 274 and 247 ℃, and T 95 was 269 ℃ for SCM-2 (Table S2), among which, SCM-2 exhibited the highest catalytic performance (Fig. 5 (a)), mainly attributing to the strong oxygen storage and release capacity of CeO 2 . The doped Co promoted the formation of O V s, which enhanced CB adsorption on surface O V s and facilitated in-depth oxidation by Mn 4+ /Mn 3+ . Surface oxygen species and low-temperature reducibility were key factors influencing the catalytic performance of manganate materials. The comparison of catalytic performance and characterization results revealed a significant correlation between specific surface area, surface oxygen species, low-temperature reducibility and CB oxidation performance. Therefore, the high surface oxygen concentration, excellent low-temperature reducibility and unique structure of SCM-2 contributed to its superior CB catalytic combustion performance. The large surface area of SCM-2 not only enhanced CB adsorption on the catalyst surface but also increased the contact area between the material and CB, thereby accelerating the CB oxidation reaction. Figure 5 (b) showed that at a dosage of 100 mg of catalyst, the removal effect was poor, as the catalyst dosage was insufficient to treat 4000 mg m –3 of CB under the given reaction conditions. The effect of different GHSV values on toluene conversion was also examined (Fig. 5 (c)). The degradation profiles of CB showed little variation with increasing reaction airspeed. For the SCM-2 sample, the T 50 and T 90 values were 171 and 247 ℃ at GHSV = 70.15 g airflow g cat –1 h –1 , respectively. The T 50 and T 90 values decreased by 10 and 19 ℃, respectively, compared to GHSV = 140.29 g airflow g cat –1 h –1 . The performance increased as the GHSV decreased from 210.44 g airflow g cat –1 h –1 to 35.07 g airflow g cat –1 h –1 . Thus, the catalytic performance of CB oxidation is strongly influenced by the GHSV value. As the GHSV decreased, the oxidation capacity of CB increased. At a water vapor content of 2.5 v/v%, the relative humidity (RH) reaches 100%. Additional experiments were conducted by introducing 2.5 v/v% water vapor between the 4th and 9th hours of a 12-hour continuous test, with dry conditions applied otherwise. The CB conversion rate remained stable, confirming the material's strong water resistance. This performance was attributed to the hydrophobic properties and stable active sites, which mitigate water-induced deactivation (Fig. 5 (d)). It could be seen that the catalyst maintains high values for conversion under both dry and wet conditions, indicating that water vapor has little effect on its performance (showed in Fig.S2). Figure 5 (e) showed that as the CB concentration increases, the removal rate curve shifted to higher temperatures, with minimal change in the T 90 value. This indicated that the catalyst has a sufficient number of active sites to maintain high catalytic performance. The Ce-doped material, SCM-2, exhibited enhanced catalytic performance compared to other reports (Table S3). To demonstrate the stability of the SCM-2 catalyst, a cycling test was performed (Fig S1 ). In the cycling test, the catalyst was reused five times. The removal efficiency for CB remained high from 300 ℃ onward and showed little change over the five cycles. SCM-2 was subjected to a continuous long-duration operation test with an initial CB concentration of 4000 mg m –3 , an airspeed of 70.15 g airflow g cat –1 h –1 and a reaction temperature of 300 ℃ (Fig. 5 (g)). The analysis results showed that the catalytic combustion efficiency of CB by SCM-2 remained high after 168 hours of testing, with no significant decrease in catalytic performance. These results indicated that the catalyst has high stability in continuous reactions, making it suitable for industrial catalytic applications. The microstructures of SCM-0 and SCM-2 showed no significant difference between before and after use. The structures of both had not changed significantly after catalytic combustion of CB, indicating that these materials exhibit structural stability. 3.3 Mechanistic Analyses To further investigate the mechanism of by-product generation during toluene degradation by SCM-2, the tail gas from 30 minutes of CB treatment was analyzed by GC-MS after stabilizing at 300 ℃ for 180 minutes. The results in Fig. 7 showed that the untreated gas was dominated by CB and also contained octane and 1-pyrazolidinecarboxamide. The intermediate products during CB degradation by SCM-2 included propane, tetrachloroethene, 2(1H)-pyrimidinone and octane. Additionally, the figure showed that the CB content ratio before and after treatment was 7.2%, which was consistent with the CB conversion and mineralization data obtained with the SCM-2 catalyst. 4 CONCLUSIONS This study showed that Ce doping of the A-site in SrMnO 3 increased surface defects and the smaller grain size of the material contributed to a larger specific surface area, better low-temperature reducibility, more active sites and a higher concentration of O V s, which accelerated the reduction of Mn 4+ /Mn 3+ and preserved enough active sites for further CB oxidation, preventing chlorine toxicity and improving catalytic performance (T 90 = 247 ℃, T 95 = 269 ℃, mineralization rate = 71%). GC-MS analysis showed that the efficient catalytic degradation inhibited the generation of intermediates and the attachment to the catalyst surface, which helped maintain stable catalytic performance. This work presented an efficient strategy for preparing metal oxide catalysts with more defects, suitable for VOCs oxidation and other oxidation reactions. Declarations Ethics, Consent to Participate, and Consent to Publish declarations Not applicable Conflict of Interest Statement The authors of this paper declare no conflicts of interest. Author Contribution Peng Yu: Conceptualization, Data curation, Software, Method, Writing-Original Draft, Writing-Reviewing and Editing; Jing Shi: Data curation, Investigation; Hangjiang Wan: Data curation, Investigation; Zijian Tang: Data Curation, Investigation; Kangyu Yuan: Data Curation; Xiao Zhang: Methodology, Software; Yanhua Xu: Resources; Xi Li: Supervision; Yongjun Sun: Conceptualization, Funding acquisition, Supervision, Writing-Reviewing and Editing. Acknowledgement This work was supported by the National Key Research and Development Program of China (No. 2017YFB0602500 & No. 2024YFB4105502-4), National Natural Science Foundation of China (No. 51508268), Natural Science Foundation of Jiangsu Province in China (No. BK20201362 & No. BK20240569), 2018 Six Talent Peaks Project of Jiangsu Province (JNHB-038), Natural Science Foundation of the Jiangsu Higher Education Institutions of China (1020241966). Science and Technology Major Project of Shanxi Province (MH2015-08). References Acharya, S., Swain, G., Parida, K.M. (2020). MoS 2 -mesoporous LaFeO 3 hybrid photocatalyst: Highly efficient visible-light driven photocatalyst. International Journal of Hydrogen Energy 45, 11502–11511. https://doi.org/https://doi.org/10.1016/j.ijhydene.2020.01.158 Acosta Perez, H., Lopez, C.A., Furlong, O.J., Nazzarro, M.S., Marchetti, S.G., Cadus, L.E., Aguero, F.N. (2023). 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Constructing CsPbBr 3 Cluster Passivated-Triple Cation Perovskite for Highly Efficient and Operationally Stable Solar Cells. Advanced Functional Materials 29, 1809180. https://doi.org/https://doi.org/10.1002/adfm.201809180 Zhu, J., Thomas, A. (2009). Perovskite-type mixed oxides as catalytic material for NO removal. Applied Catalysis B: Environmental 92, 225–233. https://doi.org/https://doi.org/10.1016/j.apcatb.2009.08.008 Zhu, W., Chen, X., Liu, Z., Liang, C. (2020). Insight into the Effect of Cobalt Substitution on the Catalytic Performance of LaMnO 3 Perovskites for Total Oxidation of Propane. The Journal of Physical Chemistry C 124, 14646–14657. https://doi.org/10.1021/acs.jpcc.0c03084 Zhu, X., Zhang, S., Yang, Y., Zheng, C., Zhou, J., Gao, X., Tu, X. (2017). Enhanced performance for plasma-catalytic oxidation of ethyl acetate over La1 -x Ce x CoO 3+δ catalysts. Applied Catalysis B: Environmental 213, 97–105. https://doi.org/https://doi.org/10.1016/j.apcatb.2017.04.066 Additional Declarations No competing interests reported. Supplementary Files Revisedsupplementarydata.docx Cite Share Download PDF Status: Under Review Version 1 posted Reviews received at journal 28 Apr, 2025 Reviewers agreed at journal 22 Apr, 2025 Reviews received at journal 22 Apr, 2025 Reviewers agreed at journal 22 Apr, 2025 Reviewers invited by journal 22 Apr, 2025 Submission checks completed at journal 22 Apr, 2025 First submitted to journal 21 Apr, 2025 You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. 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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-5995427","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":446237779,"identity":"bff7f9d8-52b5-45de-92f4-696056a2483b","order_by":0,"name":"Peng Yu","email":"","orcid":"","institution":"Nanjing Tech University","correspondingAuthor":false,"prefix":"","firstName":"Peng","middleName":"","lastName":"Yu","suffix":""},{"id":446237780,"identity":"94ac2f1f-dca2-4490-b4c5-48dff8299941","order_by":1,"name":"Jing Shi","email":"","orcid":"","institution":"Nanjing Tech 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evaluation.\u003c/p\u003e","description":"","filename":"image1.png","url":"https://assets-eu.researchsquare.com/files/rs-5995427/v1/6dae9e1c5ad2ceee4638b6ba.png"},{"id":81206487,"identity":"d0b7b88a-722f-4c79-935c-6de9e8e9f638","added_by":"auto","created_at":"2025-04-23 12:22:43","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":2673015,"visible":true,"origin":"","legend":"\u003cp\u003eXRD patterns and FTIR spectra of the synthesized catalysts.\u003c/p\u003e","description":"","filename":"image2.png","url":"https://assets-eu.researchsquare.com/files/rs-5995427/v1/ef9f280bd29eeb3dd894e79c.png"},{"id":81206485,"identity":"e9d082ad-dfbc-4f9b-81b2-385c6afecd3b","added_by":"auto","created_at":"2025-04-23 12:22:43","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":5209166,"visible":true,"origin":"","legend":"\u003cp\u003eSynthesis process of the catalysts (a); SEM (b, c) and TEM (d, e) images of SCM-0; SEM (f, g), TEM (h, i) and EDS-mapping (j, k), l, m, n) images of SCM-2.\u003c/p\u003e","description":"","filename":"image3.png","url":"https://assets-eu.researchsquare.com/files/rs-5995427/v1/03daf8be5c08b091f83403da.png"},{"id":81207308,"identity":"1fe9aa35-5602-43e9-8bd4-17ef2a4d1a90","added_by":"auto","created_at":"2025-04-23 12:30:43","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":19425546,"visible":true,"origin":"","legend":"\u003cp\u003eXPS spectra (a, b, c, d), H\u003csub\u003e2\u003c/sub\u003e-TPR (e) and NH\u003csub\u003e3\u003c/sub\u003e-TPD (f) of SCM-0 and SCM-2.\u003c/p\u003e","description":"","filename":"image4.png","url":"https://assets-eu.researchsquare.com/files/rs-5995427/v1/8343d06b7716c96a60a8ead7.png"},{"id":81206493,"identity":"745d1052-6769-462a-81c2-8fd888a5ad67","added_by":"auto","created_at":"2025-04-23 12:22:43","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":26523886,"visible":true,"origin":"","legend":"\u003cp\u003eInfluence of different catalysts (a), catalyst dosage (b), air velocity (c), water-resistance (d), and pollutant concentration (e) on CB degradation with SCM-2; stability comparison among quartz, SCM-0 and SCM-2 (f).\u003c/p\u003e","description":"","filename":"image5.png","url":"https://assets-eu.researchsquare.com/files/rs-5995427/v1/4e9ce0b4904d32701d3265de.png"},{"id":81206491,"identity":"7b4539a9-8ead-44cb-a0b5-87e3eaae1e1e","added_by":"auto","created_at":"2025-04-23 12:22:43","extension":"jpeg","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":461984,"visible":true,"origin":"","legend":"\u003cp\u003eSEM images of used SCM-2 (a, b, c) and SCM-0 (d, e, f).\u003c/p\u003e","description":"","filename":"image6.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-5995427/v1/5fd8d1ccc588ad4b0933b500.jpeg"},{"id":81206503,"identity":"967a893a-405e-49d1-8f8d-2fe846e27b33","added_by":"auto","created_at":"2025-04-23 12:22:43","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":389086,"visible":true,"origin":"","legend":"\u003cp\u003eGC-MS spectrum of CB degradation by SCM-2.\u003c/p\u003e","description":"","filename":"image7.png","url":"https://assets-eu.researchsquare.com/files/rs-5995427/v1/a3c1a85b2e0f874f629de19d.png"},{"id":81208428,"identity":"1f43414b-5a39-4961-8313-e2bcbc0fb3b0","added_by":"auto","created_at":"2025-04-23 12:47:11","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":51196336,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-5995427/v1/05c13b9b-c9d0-4db4-8ca0-4b2230bb2bb2.pdf"},{"id":81206497,"identity":"90998ffd-fa8b-417b-9cc6-e830dbbd5390","added_by":"auto","created_at":"2025-04-23 12:22:43","extension":"docx","order_by":0,"title":"","display":"","copyAsset":false,"role":"supplement","size":2802952,"visible":true,"origin":"","legend":"","description":"","filename":"Revisedsupplementarydata.docx","url":"https://assets-eu.researchsquare.com/files/rs-5995427/v1/8b8585d7890cb5e97d2e2845.docx"}],"financialInterests":"No competing interests reported.","formattedTitle":"Contribution of multi-metal oxides based on SrMnO 3 for the enhanced formation of Ov on chlorobenzene degradation: performance and mechanism","fulltext":[{"header":"1 INTRODUCTION","content":"\u003cp\u003eVolatile organic compounds (VOCs) are major precursors of O\u003csub\u003e3\u003c/sub\u003e and PM\u003csub\u003e2.5\u003c/sub\u003e, emitted in large quantities that pose a serious threat to human health and the environment (He et al., \u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e2019\u003c/span\u003e; Xiao et al., \u003cspan citationid=\"CR39\" class=\"CitationRef\"\u003e2022\u003c/span\u003e). As a significant subclass of VOCs, chlorinated volatile organic compounds (CVOCs), are emitted through volatilization and leakage during industrial, agricultural and pharmaceutical production processes. These pollutants are often difficult to biodegrade and some are \u0026ldquo;carcinogenic, mutagenic and teratogenic\u0026rdquo; to humans. Typically, catalytic combustion technology is commonly used for CVOCs treatment due to its wide application range, low oxidation temperature and low energy consumption. However, the chlorosis of catalysts, caused by chlorine-containing species generates during CVOCs degradation, significantly limits the further application of this technology. Therefore, it is crucial to develop high-performance catalysts for the catalytic combustion of CVOCs to minimize chlorosis and the formation of secondary toxic by-products.\u003c/p\u003e \u003cp\u003ePerovskites consist of isolated metal halide octahedral anions surrounded by organic or inorganic cations, with excitons strongly confined to each octahedron (Sun et al., \u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e2021\u003c/span\u003e). Crystal defects (e.g., vacancies) in perovskite provide channels for ion migration during the catalytic combustion process (Zhou et al., \u003cspan citationid=\"CR44\" class=\"CitationRef\"\u003e2019\u003c/span\u003e). These defects promote the migration and reaction of oxygen ions, enhancing oxygen mobility and facilitating the efficient degradation of CVOCs (Choudhary et al., \u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e2002\u003c/span\u003e; G\u0026eacute;lin and Primet, \u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e2002\u003c/span\u003e; Royer et al., \u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e2014\u003c/span\u003e). However, the performance of perovskite for pollutant degradation mainly depends on the rational design and modulation of its structure-function relationship and surface properties (Blasin-Aub\u0026eacute; et al., \u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e2003\u003c/span\u003e). For a typical perovskite catalyst, the A-site cation only stabilizes the structure with no catalysis process occurring, while A/B-site doping of perovskites would alter the physicochemical property and the performance of the catalyst (Zhu and Thomas, \u003cspan citationid=\"CR45\" class=\"CitationRef\"\u003e2009\u003c/span\u003e; Onrubia-Calvo et al., \u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e2017\u003c/span\u003e; Yang and Teng, 2018). It has been reported that the incorporation of Cs\u003csup\u003e+\u003c/sup\u003e in δ-CsPbI\u003csub\u003e3\u003c/sub\u003e provides alternative phase transition pathways to the perovskite phase and creates sparse nucleation centers for further crystal growth (Qin et al., \u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e2020\u003c/span\u003e). Additionally, doping of A-site cations would promote the valence transformation of B-site element. Studies using techniques such as XRD, BET, XPS and H\u003csub\u003e2\u003c/sub\u003e-TPR have revealed changes in the oxidation states of the B-site cation Mn, as well as alterations in the overall redox properties of perovskite due to A-site substitution (Rezlescu et al., \u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e2014\u003c/span\u003e; Doggali et al., \u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e2015\u003c/span\u003e). La- or Sr-based perovskites containing Co, Fe, or Mn as the M cation exhibited great performance in catalytic combustion, while the manganese-based perovskites exhibited high performance and cost-effectiveness (Arai et al., \u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e1986\u003c/span\u003e). Manganese-based perovskites are cost-effective, exhibit high catalytic performance and effectively promote catalytic combustion reactions (Rezlescu et al., \u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e2014\u003c/span\u003e; Eom et al., \u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e2018\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eThe rare-earth element Ce has garnered increasing attention in catalysis due to its unique electron arrangement (Raabe et al., \u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e2012\u003c/span\u003e; Qian et al., \u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e2020b\u003c/span\u003e). The introduction of Ce ions alters the charge distribution of the catalyst, compensates for charge imbalances, induces the formation of oxygen vacancies (O\u003csub\u003eV\u003c/sub\u003es) and promotes the valence cycling of B-site element. Optimal rare earth doping stabilizes the lattice structure and reduces the formation energy of O\u003csub\u003eV\u003c/sub\u003es, as well as the energy for oxygen adsorption and dissociation, thereby enhancing catalytic performance (Zhang et al., \u003cspan citationid=\"CR42\" class=\"CitationRef\"\u003e2020a\u003c/span\u003e). When the molar ratio of Ce in (La\u0026thinsp;+\u0026thinsp;Ce) exceeds 0.4, Ce readily incorporates into the LaFeO\u003csub\u003e3\u003c/sub\u003e structure, facilitating the catalytic combustion reaction (Ovejero et al., \u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e2012\u003c/span\u003e). Sun et al. found that, the increased content of Ce facilitated the formation of O\u003csub\u003eV\u003c/sub\u003es in La\u003csub\u003e1\u0026thinsp;\u0026minus;\u0026thinsp;x\u003c/sub\u003eCe\u003csub\u003ex\u003c/sub\u003eFeO\u003csub\u003e3\u0026minus;δ\u003c/sub\u003e with oxygen adsorbing on O\u003csub\u003eV\u003c/sub\u003es to form reactive oxygen species. (Sun et al., \u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e2019\u003c/span\u003e). In addition, cerium oxide would also introduce additional O\u003csub\u003eV\u003c/sub\u003es into the catalyst. Yuan et al. found that CeO\u003csub\u003e2\u003c/sub\u003e, generated after Ce doping, would store or release O\u003csub\u003e2\u003c/sub\u003e through Ce\u003csup\u003e4+\u003c/sup\u003e/Ce\u003csup\u003e3+\u003c/sup\u003e redox pairs (Yuan et al., \u003cspan citationid=\"CR41\" class=\"CitationRef\"\u003e2012\u003c/span\u003e; Nasirian et al., \u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e2017\u003c/span\u003e). Besides, the O\u003csub\u003eV\u003c/sub\u003es on the CeO\u003csub\u003e2\u003c/sub\u003e surface would also enhance O\u003csub\u003e2\u003c/sub\u003e adsorption. Qian et al. found that the introduction of Ce into the A cation of LaCoO\u003csub\u003e3\u003c/sub\u003e enhanced the catalytic performance in oxygen precipitation and reduction reactions (OER/ORR) (Qian et al., \u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e2020a\u003c/span\u003e), which also promoted a higher number of O\u003csub\u003eV\u003c/sub\u003es and Co\u003csup\u003e3+\u003c/sup\u003e/Co\u003csup\u003e2+\u003c/sup\u003e and Ce\u003csup\u003e4+\u003c/sup\u003e/Ce\u003csup\u003e3+\u003c/sup\u003e redox pairs to enhance the performance of CB combustion (Zhu and Thomas, \u003cspan citationid=\"CR45\" class=\"CitationRef\"\u003e2009\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eIn this study, a SrMnO\u003csub\u003e3\u003c/sub\u003e-based multi-metal oxide catalyst was designed and synthesized, with Ce incorporated to increase the defectivity and stability of catalyst to ensure catalytic performance even after the occupation of active sites by chlorine species. Various characterizations were performed to investigate the morphological structure and chemical composition of the catalysts. Influences of pollutant concentration, catalyst dosing, airflow speed and relative humidity were systematically investigated. The catalytic degradation mechanism was inferred by identifying the major substances generated in the degradation process. Possible degradation pathways and the environmental toxicity of intermediates were further assessed through intermediate product analysis (GC-MS).\u003c/p\u003e"},{"header":"2 METHODS","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003e2.1 Chemicals and materials\u003c/h2\u003e \u003cp\u003eAll the chemicals and reagents in this work were analytical-grade or high-performance gas chromatography (HPGC) grade reagents without any purification. Strontium acetate hemihydrate (Sr(CH\u003csub\u003e3\u003c/sub\u003eCO\u003csub\u003e2\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e\u0026middot;0.5 H\u003csub\u003e2\u003c/sub\u003eO), cerium nitrate hexahydrate (Ce(NO\u003csub\u003e3)3\u003c/sub\u003e\u0026middot;6H\u003csub\u003e2\u003c/sub\u003eO), manganese acetate tetrahydrate (Mn(CH\u003csub\u003e3\u003c/sub\u003eCOO)\u003csub\u003e2\u003c/sub\u003e\u0026middot;4 H\u003csub\u003e2\u003c/sub\u003eO), KOH were all purchased from Sinopharm Chemical Reagents Co., Ltd. (Nanjing, China). CB was provided by Aladdin Chemical Co., Ltd (Shanghai, China). Deionized water used throughout all experiments were generated by water purification instrument (GWB-UP, Persee, China). The tap water was supplied by Nanjing Chemical Industrial Park Water Industry Co., Ltd. (Nanjing, China).\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec4\" class=\"Section2\"\u003e \u003ch2\u003e2.2 Preparation of catalysts\u003c/h2\u003e \u003cp\u003eA series of Sr-Ce-Mn-Ox catalysts were synthesized using a hydrothermal method (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e(a)). Strontium acetate hemihydrate, cerium nitrate hexahydrate and manganese acetate tetrahydrate were weighed in specific molar ratios and sequentially dissolved in purified water (20 mL). KOH solution (5 M) was added dropwise to the homogeneous solution and the pH was adjusted to 13.5\u0026thinsp;\u0026plusmn;\u0026thinsp;0.5. The solution was then transferred to a 100 mL high-pressure reactor and reacted at 180 ℃ for 16 hours. Finally, the resulting materials were washed with purified water to neutrality and dried overnight. The materials were labeled as SCM-0, SCM-1, SCM-2, SCM-3, SCM-4 and SCM-5 in a specific order (Table \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003e).\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec5\" class=\"Section2\"\u003e \u003ch2\u003e2.3 Characterization method\u003c/h2\u003e \u003cp\u003e \u003cdiv class=\"BlockQuote\"\u003e \u003cp\u003eMorphology investigation was recorded by scanning electron microscope (SEM, Supra 55, Carl Zeiss, Germany). Transmission electron microscope (TEM) and high-resolution TEM (HRTEM) were performed on a JEM-200CX instrument (JEOL, Japan) with energy disperse spectroscopy (EDS) applied to analysis the elemental composition and distribution. X-ray diffraction (XRD) analysis was carried out on a DMAX-2400 diffractometer (Rigaku, Japan) at 40 kV and 40 mA with Cu Kα radiation (λ\u0026thinsp;=\u0026thinsp;0.15406 \u0026Aring;). The elemental composition and oxidation states were obtained by a Nexsa X-ray photoelectron spectroscopy (XPS, Thermo Fisher, USA) and all the binding energies were calibrated with the peak of 284.8 eV on the C 1s spectrum with detailed information presented in Text S1 of supporting information. H\u003csub\u003e2\u003c/sub\u003e-temperature programmed reduction (H\u003csub\u003e2\u003c/sub\u003e-TPR), O\u003csub\u003e2\u003c/sub\u003e-temperature programmed desorption (O\u003csub\u003e2\u003c/sub\u003e-TPD) and NH\u003csub\u003e3\u003c/sub\u003e-temperature programmed desorption (NH\u003csub\u003e3\u003c/sub\u003e-TPD) were performed on a Temperature programmed chemical adsorption analyzer (Micromeritics AutoChem II 2920 instrument, America).\u003c/p\u003e \u003c/div\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec6\" class=\"Section2\"\u003e \u003ch2\u003e2.4 Catalytic evaluation\u003c/h2\u003e \u003cp\u003eFor the catalytic performance test, CB was selected as the characteristic pollutant. A mixture of 100 mg of catalyst and 800 mg of quartz sand was placed in a quartz tube (6 mm in diameter), sealed with quartz cotton at both ends and heated in a tube furnace. The furnace temperature could be programmatically controlled and the reaction temperature was monitored (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e). The reaction temperature ranged from 30 to 300 ℃, with temperature points at 30 ℃ and 60 ℃, and a 50 ℃ gradient from 100 ℃ to 300 ℃ every 50 minutes. Performance data were recorded once the reaction reached a steady state (after stabilizing for 40 minutes) for CB gas concentration. The inlet gas concentration and humidity were controlled using a micro syringe pump and gas generator. The CB concentration was maintained at approximately 4000 mg m\u003csup\u003e\u0026ndash;3\u003c/sup\u003e, with O\u003csub\u003e2\u003c/sub\u003e (21 vol.%) and N\u003csub\u003e2\u003c/sub\u003e as the equilibrium gases. The total gas flow rate was 100 mL min\u003csup\u003e\u0026ndash;1\u003c/sup\u003e and the airflow rate was 70.15 g \u003csub\u003eairflow\u003c/sub\u003e g \u003csub\u003ecat\u003c/sub\u003e\u003csup\u003e\u0026ndash;1\u003c/sup\u003e h\u003csup\u003e\u0026ndash;1\u003c/sup\u003e. A methane conversion furnace was used to convert the outlet gas into CO\u003csub\u003e2\u003c/sub\u003e and the mineralization rate of the pollutants was then calculated.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e"},{"header":"3 RESULTS AND DISCUSSION","content":"\u003cdiv id=\"Sec8\" class=\"Section2\"\u003e \u003ch2\u003e3.1 Characterization\u003c/h2\u003e \u003cp\u003eThe X-ray diffraction (XRD) patterns of the synthesized catalysts were exhibited in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e(a). The phase compositions of the catalysts with different metal doping ratios were similar and the materials primarily consisted of SrMnO\u003csub\u003e3\u003c/sub\u003e, CeO\u003csub\u003e2\u003c/sub\u003e, SrO and MnO\u003csub\u003e2\u003c/sub\u003e. The XRD peaks of the samples in the 2θ range from 5\u0026deg; to 80\u0026deg; corresponded well to those of the SrMnO\u003csub\u003e3\u003c/sub\u003e standard card (JCPDS No. 00-025-0900), indicating that the resulting catalyst conforms to the perovskite crystal structure. The sample's crystal structure was orthorhombic. Characteristic diffraction peaks of CeO\u003csub\u003e2\u003c/sub\u003e and MnO\u003csub\u003e2\u003c/sub\u003e appeared at 2θ\u0026thinsp;=\u0026thinsp;28.56\u0026deg;, 33.08\u0026deg;, 47.49\u0026deg;, 56.33\u0026deg; and 2θ\u0026thinsp;=\u0026thinsp;21.82\u0026deg;, 35.17\u0026deg;, respectively. Thus, it could be concluded that the chalcogenide-type catalysts were successfully prepared, with SrO, MnO\u003csub\u003e2\u003c/sub\u003e, Mn\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e and CeO\u003csub\u003e2\u003c/sub\u003e being produced during synthesis, consistent with the TEM characterization results. Absorption bands for Mn-O stretching vibrations in the catalyst series were observed at 633, 529 and 420 cm\u003csup\u003e\u0026ndash;1\u003c/sup\u003e (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e(b)). The Ce-O vibrational bands likely overlapped with those at 529 cm\u003csup\u003e\u0026ndash;1\u003c/sup\u003e and did not appear separately. Bands at 569 and 689 cm\u003csup\u003e\u0026ndash;1\u003c/sup\u003e were consistent with the Ce-O stretching vibrational mode, resulting from the partial reduction of Ce\u003csup\u003e4+\u003c/sup\u003e to Ce\u003csup\u003e3+\u003c/sup\u003e. The stretching vibrations of Ce-O-Ce bonds were observed at 551 cm\u003csup\u003e\u0026ndash;1\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eFigure\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e showed the microscopic morphology of the samples. After doping with Ce, the surface morphology changed from stacked clusters in SCM-0 to smaller, more dispersed clusters in SCM-2. A comparison of Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e(c) and Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e(g) revealed a decrease in particle size, accompanied by an increase in specific surface area (37.46 m\u003csup\u003e2\u003c/sup\u003e g\u003csup\u003e\u0026ndash;1\u003c/sup\u003e for SCM-0 to 76.76 m\u003csup\u003e2\u003c/sup\u003e g\u003csup\u003e\u0026ndash;1\u003c/sup\u003e for SCM-2). The N\u003csub\u003e2\u003c/sub\u003e adsorption-desorption isotherms and pore size distributions (Fig. \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003e), along with the surface area and pore structure results (Table S2), were consistent with the SEM image data. The results indicated that the changes in morphology and surface area of the Ce metal-doped materials were due to the CeO\u003csub\u003e2\u003c/sub\u003e formed during synthesis. The presence of Ce\u003csup\u003e3+\u003c/sup\u003e and Ce\u003csup\u003e4+\u003c/sup\u003e exacerbated lattice distortion (Zhang et al., \u003cspan citationid=\"CR43\" class=\"CitationRef\"\u003e2020b\u003c/span\u003e; Jiang et al., \u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e2023\u003c/span\u003e), which significantly increased the surface area. This suggested that Ce introduction into the chalcogenide lattice raises the concentration of O\u003csub\u003eV\u003c/sub\u003es (Ansari et al., \u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e2020\u003c/span\u003e). Generally, a high specific surface area increased the number of active surface sites, making it easier for reactant molecules to adsorb onto the catalyst surface. This facilitated deeper oxidation and improved the catalyst\u0026rsquo;s performance (Ding et al., \u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e2016\u003c/span\u003e; Li et al., \u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e2022\u003c/span\u003e; Liu et al., \u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e2022\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eThe specific substances in SCM-0 and SCM-2 were characterized by TEM-EDS and the results were presented below. Figure\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e(d, e, h, i) clearly showed that the four substances, SrMnO\u003csub\u003e3\u003c/sub\u003e, MnO\u003csub\u003e2\u003c/sub\u003e, Mn\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e and SrO, were present in both samples. The key difference was that SCM-2 contained more CeO\u003csub\u003e2\u003c/sub\u003e, confirming that CeO\u003csub\u003e2\u003c/sub\u003e was generated during the synthesis of the Ce-metal doped sample SCM-2.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eXPS spectra provided precise information about the surface elemental composition, metal oxidation states and adsorbed species of solid materials. Figure\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e presented the Sr 3d, Ce 3d, Mn 2p and O1s XPS spectra for both samples. Mn\u003csup\u003e3+\u003c/sup\u003e and Mn\u003csup\u003e4+\u003c/sup\u003e species were present on the surface of both samples, along with surface lattice oxygen (O\u003csub\u003elatt\u003c/sub\u003e) and adsorbed oxygen (O\u003csub\u003eads\u003c/sub\u003e, e.g., O\u003csup\u003e2\u0026ndash;\u003c/sup\u003e, O\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e2\u0026ndash;\u003c/sup\u003e and O\u003csup\u003e\u0026ndash;\u003c/sup\u003e). The atomic ratios of Mn\u003csup\u003e4+\u003c/sup\u003e/Mn\u003csup\u003e3+\u003c/sup\u003e and O\u003csub\u003elatt\u003c/sub\u003e/O\u003csub\u003eads\u003c/sub\u003e on the surface significantly affected the catalytic oxidation performance of manganates for VOCs (Boningari et al., \u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e2015\u003c/span\u003e; Chen et al., \u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e2019\u003c/span\u003e). Figure\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e(e) showed the Mn 2p \u003csub\u003e3/2\u003c/sub\u003e XPS spectra of SCM-2 samples at BE\u0026thinsp;=\u0026thinsp;641.4, 642.6 and 643.9 eV, which could be decomposed into three components corresponding to surface Mn\u003csup\u003e2+\u003c/sup\u003e, Mn\u003csup\u003e4+\u003c/sup\u003e and Mn\u003csup\u003e3+\u003c/sup\u003e species, respectively (Alifanti et al., \u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e2003\u003c/span\u003e; Li et al., \u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e2019a\u003c/span\u003e; Zhu et al., \u003cspan citationid=\"CR46\" class=\"CitationRef\"\u003e2020\u003c/span\u003e). SCM-2 exhibited a lower Mn\u003csup\u003e4+\u003c/sup\u003e/Mn\u003csup\u003e3+\u003c/sup\u003e molar ratio on the surface compared to SCM-0, likely due to the conversion of Mn\u003csup\u003e4+\u003c/sup\u003e to Mn\u003csup\u003e3+\u003c/sup\u003e during the catalytic oxidation of CB. A specific Mn\u003csup\u003e4+\u003c/sup\u003e/Mn\u003csup\u003e3+\u003c/sup\u003e molar ratio correlated with lattice defects, promoting the redox properties of chalcogenides and enhancing catalytic performance (Di Benedetto et al., \u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e2022\u003c/span\u003e). The peaks at 882.6 eV and 901.2 eV corresponded to Ce\u003csup\u003e3+\u003c/sup\u003e, associated with the Ce 3d \u003csub\u003e5/2\u003c/sub\u003e and Ce 3d \u003csub\u003e3/2\u003c/sub\u003e states, respectively. The peak at 898.5 eV corresponded to Ce\u003csup\u003e2+\u003c/sup\u003e and the peaks at 883.8, 907.7 and 917.0 eV correspond to Ce\u003csup\u003e4+\u003c/sup\u003e (Wang et al., \u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e2014\u003c/span\u003e; Meng et al., \u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e2018\u003c/span\u003e). The results indicated that Ce\u003csup\u003e2+\u003c/sup\u003e, Ce\u003csup\u003e3+\u003c/sup\u003e and Ce\u003csup\u003e4+\u003c/sup\u003e coexisted on the catalyst surface. The formation of Ce\u003csup\u003e3+\u003c/sup\u003e promoted the generation of O\u003csub\u003eV\u003c/sub\u003es, with higher Ce\u003csup\u003e3+\u003c/sup\u003e concentrations leading to a greater O\u003csub\u003eV\u003c/sub\u003es concentration on the catalyst surface (Acharya et al., \u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e2020\u003c/span\u003e). Performance tests showed that the Ce-doped SCM-2 samples exhibited the highest performance, suggesting that Ce\u003csup\u003e3+\u003c/sup\u003e in the catalyst positively contributes to the reaction catalysis. The O1s spectra for each sample at BE\u0026thinsp;=\u0026thinsp;529.9, 531.6 and 533.8 eV could be decomposed into three components: O\u003csub\u003elatt\u003c/sub\u003e, O\u003csub\u003eads\u003c/sub\u003e (She et al., \u003cspan citationid=\"CR35\" class=\"CitationRef\"\u003e2018\u003c/span\u003e; Jiang et al., \u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e2019\u003c/span\u003e) and surface carbonate (CO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e2\u0026ndash;\u003c/sup\u003e). O\u003csub\u003elatt\u003c/sub\u003e primarily served as the oxidizing species, while O\u003csub\u003eads\u003c/sub\u003e replenished consumed O\u003csub\u003elatt\u003c/sub\u003e. CeO\u003csub\u003e2\u003c/sub\u003e, due to its strong oxygen storage capacity, had a higher O\u003csub\u003elatt\u003c/sub\u003e content than other catalysts (Table S2), resulting in the best CB oxidation performance. Thermodynamically, the C-Cl bond in CB had a lower bond energy, making it easier to break. CB was typically adsorbed and dissociated on surface active sites through nucleophilic attack on the C-Cl bond. The adsorbed material subsequently reacted with reactive oxygen species to form CO\u003csub\u003e2\u003c/sub\u003e and H\u003csub\u003e2\u003c/sub\u003eO. Simultaneously, the adsorbed dissociated Cl- was oxidized to Cl\u003csub\u003e2\u003c/sub\u003e by surface-active oxygen via the Deacon reaction (2 HCl\u0026thinsp;+\u0026thinsp;O\u003csub\u003e2\u003c/sub\u003e \u0026rarr; Cl\u003csub\u003e2\u003c/sub\u003e\u0026thinsp;+\u0026thinsp;H\u003csub\u003e2\u003c/sub\u003eO). Finally, the consumed oxygen was replenished by gas-phase oxygen adsorbed onto the O\u003csub\u003eV\u003c/sub\u003es (Biesinger et al., \u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e2011\u003c/span\u003e; Lv et al., \u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e2022\u003c/span\u003e). Therefore, O\u003csub\u003elatt\u003c/sub\u003e played a fundamental role and the catalytic performance of SCM-2 samples in CB oxidation improved with increasing surface-active oxygen concentration, particularly O\u003csub\u003elatt\u003c/sub\u003e.\u003c/p\u003e \u003cp\u003eThe redox capacity of the catalyst was measured by H\u003csub\u003e2\u003c/sub\u003e-TPR. Figure analysis showed that the fitting peaks of SCM-2 shift to a lower temperature compared to SCM-0, indicating the doped Ce enhanced the redox capacity of Mn\u003csup\u003e4+\u003c/sup\u003e/Mn\u003csup\u003e3+\u003c/sup\u003e and created a new Ce\u003csup\u003e4+\u003c/sup\u003e/Ce\u003csup\u003e3+\u003c/sup\u003e redox pair (Zhu et al., \u003cspan citationid=\"CR47\" class=\"CitationRef\"\u003e2017\u003c/span\u003e). The reduction peaks in SCM-0 at 308 ℃ and 345 ℃ were primarily attributed to the valence reduction of Mn\u003csup\u003e4+\u003c/sup\u003e to Mn\u003csup\u003e3+\u003c/sup\u003e. The reduction peak at 458 ℃ corresponded to the reduction of Mn\u003csup\u003e3+\u003c/sup\u003e to Mn\u003csup\u003e2+\u003c/sup\u003e. In SCM-2, the valence reduction peak of Mn\u003csup\u003e4+\u003c/sup\u003e to Mn\u003csup\u003e3+\u003c/sup\u003e occurred at 277 ℃, 31 ℃ lower than in SCM-0. This shift indicated that Ce doping accelerates the Mn\u003csup\u003e4+\u003c/sup\u003e/Mn\u003csup\u003e3+\u003c/sup\u003e reduction process, mainly due to the introduction of Ce\u003csup\u003e4+\u003c/sup\u003e, which increased O\u003csub\u003eV\u003c/sub\u003es concentration (Acosta Perez et al., \u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2023\u003c/span\u003e). This promoted the electron transfer, highlighting the role of Ce doping in enhancing the redox properties of the samples (Royer and Duprez, \u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e2011\u003c/span\u003e; Li et al., \u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e2019b\u003c/span\u003e). SCM-2 exhibited better low-temperature reduction performance, with earlier reduction peaks, higher H\u003csub\u003e2\u003c/sub\u003e consumption and significantly improved catalytic performance for CB. From the Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e (e), it can be seen that the SCM-0 material has two sub-peaks, the reduction peak located at 32.15 min is attributed to the reduction of Mn\u003csup\u003e4+\u003c/sup\u003e to Mn\u003csup\u003e3+\u003c/sup\u003e and the peak at 43.31 min is attributed to the reduction of Mn\u003csup\u003e3+\u003c/sup\u003e to Mn\u003csup\u003e2+\u003c/sup\u003e and the integrals were carried out to obtain the consumptions of H\u003csub\u003e2\u003c/sub\u003e as 3.16 mmol g\u003csup\u003e\u0026ndash;1\u003c/sup\u003e and 2.65 mmol g\u003csup\u003e\u0026ndash;1\u003c/sup\u003e, respectively. Similarly, the two peaks of the modified SCM-2 material appeared at 23.92 min and 33.91 min, respectively (8.23 min and 9.40 min earlier compared to SCM-0) and were analysed to give H\u003csub\u003e2\u003c/sub\u003e consumption of 1.54 mmol g\u003csup\u003e\u0026ndash;1\u003c/sup\u003e and 1.64 mmol g\u003csup\u003e\u0026ndash;1\u003c/sup\u003e. The reduction peaks at lower temperatures are attributed to the reduction of Mn\u003csup\u003e4+\u003c/sup\u003e to Mn\u003csup\u003e3+\u003c/sup\u003e, while the reduction peaks at higher temperatures are attributed to the reduction of Mn\u003csup\u003e3+\u003c/sup\u003e to Mn\u003csup\u003e2+\u003c/sup\u003e. The area ratio at both temperatures is 0.84 for the SCM-0 material and 1.06 for the SCM-2 material, suggesting that more Mn\u003csup\u003e3+\u003c/sup\u003e is reduced to Mn\u003csup\u003e2+\u003c/sup\u003e, which is consistent with the data on the increase in Mn\u003csup\u003e3+\u003c/sup\u003e content in XPS. Figure\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e(f) shows NH\u003csub\u003e3\u003c/sub\u003e-TPD profiles of SCM-0 and SCM-2 catalysts. Both the catalysts exhibited a broad multiple peak which could be separated into two components, corresponding to weak and strong acid sites, in the temperature ranges of 100\u0026ndash;200 ℃ and \u0026gt; 300℃. The NH\u003csub\u003e3\u003c/sub\u003e desorption at the weak and strong acid peaks of SCM-0 material was calculated to be 0.19 mmol g\u003csup\u003e\u0026ndash;1\u003c/sup\u003e and 0.01 mmol g\u003csup\u003e\u0026ndash;1\u003c/sup\u003e, respectively, and similarly the NH\u003csub\u003e3\u003c/sub\u003e desorption at the weak and strong acid peaks of SCM-2 material was calculated to be 0.36 mmol g\u003csup\u003e\u0026ndash;1\u003c/sup\u003e and 0.07 mmol g\u003csup\u003e\u0026ndash;1\u003c/sup\u003e, respectively. The increase of NH\u003csub\u003e3\u003c/sub\u003e desorption at the weak and strong acid peaks of the modified SCM-2 material indicates that the material has better resistance to carbon accumulation and sintering and has a high degree of carbon resistance. 0.07 mmol g\u003csup\u003e\u0026ndash;1\u003c/sup\u003e. The increased NH\u003csub\u003e3\u003c/sub\u003e desorption at the weak acid peak of the modified SCM-2 material indicates that the material has better resistance to carbon accumulation and sintering and has high selectivity to convert most of the CB into CO\u003csub\u003e2\u003c/sub\u003e and HCl, which inhibits the generation of by-products. Meanwhile, the increase of NH\u003csub\u003e3\u003c/sub\u003e desorption at the position of the strong acid peak indicates that the activity of the material is significantly improved and the reaction rate is accelerated.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec9\" class=\"Section2\"\u003e \u003ch2\u003e3.2 Catalytic performance\u003c/h2\u003e \u003cp\u003eWith no catalyst, no significant CB conversion improvement was observed below 300 ℃, indicating no homogeneous reaction occurred in the condition of CB concentration maintained at approximately 4000 mg m\u003csup\u003e\u0026ndash;3\u003c/sup\u003e, with O\u003csub\u003e2\u003c/sub\u003e (21 vol.%) and N\u003csub\u003e2\u003c/sub\u003e as the equilibrium gases. The total gas flow rate was 100 mL min\u003csup\u003e\u0026ndash;1\u003c/sup\u003e and the airflow rate was 70.15 g \u003csub\u003eairflow\u003c/sub\u003e g \u003csub\u003ecat\u003c/sub\u003e\u003csup\u003e\u0026ndash;1\u003c/sup\u003e h\u003csup\u003e\u0026ndash;1\u003c/sup\u003e). T\u003csub\u003e50\u003c/sub\u003e and T\u003csub\u003e90\u003c/sub\u003e corresponded to the reaction temperatures for CB conversions of 50% and 90%, respectively. For SCM-0 and SCM-2, T\u003csub\u003e50\u003c/sub\u003e was 194 and 171 ℃, T\u003csub\u003e90\u003c/sub\u003e was 274 and 247 ℃, and T\u003csub\u003e95\u003c/sub\u003e was 269 ℃ for SCM-2 (Table S2), among which, SCM-2 exhibited the highest catalytic performance (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e(a)), mainly attributing to the strong oxygen storage and release capacity of CeO\u003csub\u003e2\u003c/sub\u003e. The doped Co promoted the formation of O\u003csub\u003eV\u003c/sub\u003es, which enhanced CB adsorption on surface O\u003csub\u003eV\u003c/sub\u003es and facilitated in-depth oxidation by Mn\u003csup\u003e4+\u003c/sup\u003e/Mn\u003csup\u003e3+\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eSurface oxygen species and low-temperature reducibility were key factors influencing the catalytic performance of manganate materials. The comparison of catalytic performance and characterization results revealed a significant correlation between specific surface area, surface oxygen species, low-temperature reducibility and CB oxidation performance. Therefore, the high surface oxygen concentration, excellent low-temperature reducibility and unique structure of SCM-2 contributed to its superior CB catalytic combustion performance. The large surface area of SCM-2 not only enhanced CB adsorption on the catalyst surface but also increased the contact area between the material and CB, thereby accelerating the CB oxidation reaction.\u003c/p\u003e \u003cp\u003eFigure\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e(b) showed that at a dosage of 100 mg of catalyst, the removal effect was poor, as the catalyst dosage was insufficient to treat 4000 mg m\u003csup\u003e\u0026ndash;3\u003c/sup\u003e of CB under the given reaction conditions. The effect of different GHSV values on toluene conversion was also examined (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e(c)). The degradation profiles of CB showed little variation with increasing reaction airspeed. For the SCM-2 sample, the T\u003csub\u003e50\u003c/sub\u003e and T\u003csub\u003e90\u003c/sub\u003e values were 171 and 247 ℃ at GHSV\u0026thinsp;=\u0026thinsp;70.15 g \u003csub\u003eairflow\u003c/sub\u003e g \u003csub\u003ecat\u003c/sub\u003e\u003csup\u003e\u0026ndash;1\u003c/sup\u003e h\u003csup\u003e\u0026ndash;1\u003c/sup\u003e, respectively. The T\u003csub\u003e50\u003c/sub\u003e and T\u003csub\u003e90\u003c/sub\u003e values decreased by 10 and 19 ℃, respectively, compared to GHSV\u0026thinsp;=\u0026thinsp;140.29 g \u003csub\u003eairflow\u003c/sub\u003e g \u003csub\u003ecat\u003c/sub\u003e\u003csup\u003e\u0026ndash;1\u003c/sup\u003e h\u003csup\u003e\u0026ndash;1\u003c/sup\u003e. The performance increased as the GHSV decreased from 210.44 g \u003csub\u003eairflow\u003c/sub\u003e g \u003csub\u003ecat\u003c/sub\u003e\u003csup\u003e\u0026ndash;1\u003c/sup\u003e h\u003csup\u003e\u0026ndash;1\u003c/sup\u003e to 35.07 g \u003csub\u003eairflow\u003c/sub\u003e g \u003csub\u003ecat\u003c/sub\u003e\u003csup\u003e\u0026ndash;1\u003c/sup\u003e h\u003csup\u003e\u0026ndash;1\u003c/sup\u003e. Thus, the catalytic performance of CB oxidation is strongly influenced by the GHSV value. As the GHSV decreased, the oxidation capacity of CB increased. At a water vapor content of 2.5 v/v%, the relative humidity (RH) reaches 100%. Additional experiments were conducted by introducing 2.5 v/v% water vapor between the 4th and 9th hours of a 12-hour continuous test, with dry conditions applied otherwise. The CB conversion rate remained stable, confirming the material's strong water resistance. This performance was attributed to the hydrophobic properties and stable active sites, which mitigate water-induced deactivation (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e(d)). It could be seen that the catalyst maintains high values for conversion under both dry and wet conditions, indicating that water vapor has little effect on its performance (showed in Fig.S2). Figure\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e(e) showed that as the CB concentration increases, the removal rate curve shifted to higher temperatures, with minimal change in the T\u003csub\u003e90\u003c/sub\u003e value. This indicated that the catalyst has a sufficient number of active sites to maintain high catalytic performance. The Ce-doped material, SCM-2, exhibited enhanced catalytic performance compared to other reports (Table S3).\u003c/p\u003e \u003cp\u003eTo demonstrate the stability of the SCM-2 catalyst, a cycling test was performed (Fig \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003e). In the cycling test, the catalyst was reused five times. The removal efficiency for CB remained high from 300 ℃ onward and showed little change over the five cycles. SCM-2 was subjected to a continuous long-duration operation test with an initial CB concentration of 4000 mg m\u003csup\u003e\u0026ndash;3\u003c/sup\u003e, an airspeed of 70.15 g \u003csub\u003eairflow\u003c/sub\u003e g \u003csub\u003ecat\u003c/sub\u003e\u003csup\u003e\u0026ndash;1\u003c/sup\u003e h\u003csup\u003e\u0026ndash;1\u003c/sup\u003e and a reaction temperature of 300 ℃ (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e(g)). The analysis results showed that the catalytic combustion efficiency of CB by SCM-2 remained high after 168 hours of testing, with no significant decrease in catalytic performance. These results indicated that the catalyst has high stability in continuous reactions, making it suitable for industrial catalytic applications.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe microstructures of SCM-0 and SCM-2 showed no significant difference between before and after use. The structures of both had not changed significantly after catalytic combustion of CB, indicating that these materials exhibit structural stability.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec10\" class=\"Section2\"\u003e \u003ch2\u003e3.3 Mechanistic Analyses\u003c/h2\u003e \u003cp\u003eTo further investigate the mechanism of by-product generation during toluene degradation by SCM-2, the tail gas from 30 minutes of CB treatment was analyzed by GC-MS after stabilizing at 300 ℃ for 180 minutes. The results in Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003e showed that the untreated gas was dominated by CB and also contained octane and 1-pyrazolidinecarboxamide. The intermediate products during CB degradation by SCM-2 included propane, tetrachloroethene, 2(1H)-pyrimidinone and octane. Additionally, the figure showed that the CB content ratio before and after treatment was 7.2%, which was consistent with the CB conversion and mineralization data obtained with the SCM-2 catalyst.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e"},{"header":"4 CONCLUSIONS","content":"\u003cp\u003eThis study showed that Ce doping of the A-site in SrMnO\u003csub\u003e3\u003c/sub\u003e increased surface defects and the smaller grain size of the material contributed to a larger specific surface area, better low-temperature reducibility, more active sites and a higher concentration of O\u003csub\u003eV\u003c/sub\u003es, which accelerated the reduction of Mn\u003csup\u003e4+\u003c/sup\u003e/Mn\u003csup\u003e3+\u003c/sup\u003e and preserved enough active sites for further CB oxidation, preventing chlorine toxicity and improving catalytic performance (T\u003csub\u003e90\u003c/sub\u003e\u0026thinsp;=\u0026thinsp;247 ℃, T\u003csub\u003e95\u003c/sub\u003e\u0026thinsp;=\u0026thinsp;269 ℃, mineralization rate\u0026thinsp;=\u0026thinsp;71%). GC-MS analysis showed that the efficient catalytic degradation inhibited the generation of intermediates and the attachment to the catalyst surface, which helped maintain stable catalytic performance. This work presented an efficient strategy for preparing metal oxide catalysts with more defects, suitable for VOCs oxidation and other oxidation reactions.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e \u003cstrong\u003eEthics, Consent to Participate, and Consent to Publish declarations\u003c/strong\u003e \u003cp\u003eNot applicable\u003c/p\u003e \u003c/p\u003e\u003cp\u003e \u003ch2\u003eConflict of Interest Statement\u003c/h2\u003e \u003cp\u003eThe authors of this paper declare no conflicts of interest.\u003c/p\u003e \u003c/p\u003e\u003ch2\u003eAuthor Contribution\u003c/h2\u003e\u003cp\u003ePeng Yu: Conceptualization, Data curation, Software, Method, Writing-Original Draft, Writing-Reviewing and Editing; Jing Shi: Data curation, Investigation; Hangjiang Wan: Data curation, Investigation; Zijian Tang: Data Curation, Investigation; Kangyu Yuan: Data Curation; Xiao Zhang: Methodology, Software; Yanhua Xu: Resources; Xi Li: Supervision; Yongjun Sun: Conceptualization, Funding acquisition, Supervision, Writing-Reviewing and Editing.\u003c/p\u003e\u003ch2\u003eAcknowledgement\u003c/h2\u003e\u003cp\u003eThis work was supported by the National Key Research and Development Program of China (No. 2017YFB0602500 \u0026amp; No. 2024YFB4105502-4), National Natural Science Foundation of China (No. 51508268), Natural Science Foundation of Jiangsu Province in China (No. BK20201362 \u0026amp; No. BK20240569), 2018 Six Talent Peaks Project of Jiangsu Province (JNHB-038), Natural Science Foundation of the Jiangsu Higher Education Institutions of China (1020241966). Science and Technology Major Project of Shanxi Province (MH2015-08).\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eAcharya, S., Swain, G., Parida, K.M. (2020). MoS\u003csub\u003e2\u003c/sub\u003e-mesoporous LaFeO\u003csub\u003e3\u003c/sub\u003e hybrid photocatalyst: Highly efficient visible-light driven photocatalyst. International Journal of Hydrogen Energy 45, 11502\u0026ndash;11511. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/https://doi.org/10.1016/j.ijhydene.2020.01.158\u003c/span\u003e\u003cspan address=\"10.1016/j.ijhydene.2020.01.158\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eAcosta Perez, H., Lopez, C.A., Furlong, O.J., Nazzarro, M.S., Marchetti, S.G., Cadus, L.E., Aguero, F.N. (2023). 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Applied Catalysis B: Environmental 213, 97\u0026ndash;105. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/https://doi.org/10.1016/j.apcatb.2017.04.066\u003c/span\u003e\u003cspan address=\"10.1016/j.apcatb.2017.04.066\" 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":false,"email":"","identity":"aerosol-and-air-quality-research","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"","title":"Aerosol and Air Quality Research","twitterHandle":"","acdcEnabled":false,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"VoR Journals","inReviewEnabled":false,"inReviewRevisionsEnabled":false},"keywords":"Strontium manganate, Ce doping, Multi-metal oxide, Catalytic combustion","lastPublishedDoi":"10.21203/rs.3.rs-5995427/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-5995427/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eThe degradation of chlorinated volatile organic compounds (CVOCs) using conventional chalcogenide catalyst is often hindered by the accumulation of chlorine species and the loss of active sites. Although SrMnO\u003csub\u003e3\u003c/sub\u003e improves the degradation efficiency of pollutants by inhibiting chlorine species accumulation due to its high thermal stability and oxygen mobility, chlorine toxicity remains a concern. In this work, a multi-metal oxide based on SrMnO\u003csub\u003e3\u003c/sub\u003e was synthesized by hydrothermal method, with Ce introduced to increase surface deficiency, thereby exposing more active sites. The influences of catalyst dosage, relative humidity, pollutant concentration and airspeed on chlorobenzene (CB) degradation were systematically investigated, with the highest CB removal efficiency achieved by T\u003csub\u003e90\u003c/sub\u003e\u0026thinsp;=\u0026thinsp;247 ℃, T\u003csub\u003e95\u003c/sub\u003e\u0026thinsp;=\u0026thinsp;269 ℃, mineralization rate\u0026thinsp;=\u0026thinsp;71%. The catalytic mechanism was investigated with systematical characterizations and the possible degradation pathways of CB were also inferred with GC-MS. This study would provide new insights and ideas for the design and synthesis of chalcogenide-based multi-metal oxide catalyst.\u003c/p\u003e","manuscriptTitle":"Contribution of multi-metal oxides based on SrMnO 3 for the enhanced formation of Ov on chlorobenzene degradation: performance and mechanism","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-04-23 12:22:38","doi":"10.21203/rs.3.rs-5995427/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"editorInvitedReview","content":"","date":"2025-04-28T12:18:54+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"37870435380890440642368057184298890618","date":"2025-04-22T09:25:56+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-04-22T08:49:10+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"285895646913929504241350506684726598270","date":"2025-04-22T08:45:51+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2025-04-22T07:53:34+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2025-04-22T05:02:13+00:00","index":"","fulltext":""},{"type":"submitted","content":"Aerosol and Air Quality Research","date":"2025-04-22T02:04:00+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":false,"email":"","identity":"aerosol-and-air-quality-research","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"","title":"Aerosol and Air Quality Research","twitterHandle":"","acdcEnabled":false,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"VoR Journals","inReviewEnabled":false,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"d7919151-3ad3-4431-a684-7e74c31d9d35","owner":[],"postedDate":"April 23rd, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"under-review","subjectAreas":[],"tags":[],"updatedAt":"2025-04-29T20:23:11+00:00","versionOfRecord":[],"versionCreatedAt":"2025-04-23 12:22:38","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-5995427","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-5995427","identity":"rs-5995427","version":["v1"]},"buildId":"XKTyCvWXoU3ODBz1xrDgd","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}