CHEMOSPHERE
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2022
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IF 8.943
Yilin Dong,Jing Sun,Xiaoling Ma,Wenlong Wang,Zhanlong Song,Xiqiang Zhao,Yanpeng Mao,Wenxiang Li
MnO x has received widespread attention in low-temperature catalytic oxidation of VOCs, however, the synergy effect of MnO x and support on the VOCs catalytic ozonation were rarely studied. In this study, five different MnO x /X (X: MCM-41, 13X, ZSM-5, HY, USY) were synthesized and found their support greatly affect the catalytic oxidation activity. MnO x /MCM-41 presents the largest specific surface area, pore volume and unique surface morphology, and thereby provides more sites for MnO x loading and VOCs adsorption. Moreover, MnO x /MCM-41 presents a high proportion of Mn 3+ , which helps to enhance the ion exchange capability, and thus promotes the regeneration of oxygen vacancies. Furthermore, a part of Mn was proved to be introduced into the MCM-41 lattice, which can promote the electron transfer between the active components and the support, and thereby effectively improve the surface electronic properties of the catalyst. The toluene catalytic experiments showed that MnO x /MCM-41 exhibited the best catalytic activity , presenting complete degradation of O 3 and VOCs at room temperature. In addition, 5 wt%MnO x /MCM-41 exhibited better catalytic activity than other loading, and its higher surface oxygen species endowed it with strong water resistance and stability. In-situ DRIFTs indicated that toluene was initially oxidized into benzyl alcohol during the adsorption process, and then decomposed to intermediate products (benzaldehyde, phenolate, etc.) during the catalytic ozonation process, and finally oxidized to carbon dioxide. In conclusion, the supply of loading sites and the improvement of interfacial electron transfer are the manifestations of the synergy between the support and MnO x , leading to the promotion of the catalytic ozonation of VOCs.
研究领域:
环境科学
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催化材料
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DOI
PubMed
高影响因子
JOURNAL OF ENVIRONMENTAL ENGINEERING
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2025
·Vol. 151
·期 8
·04025043
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IF 1.6
Jie Zhang,Mengchen Zong,Ben Dong,Sijie Ge,Shilong He
Quinoline, as one of the typical toxic and refractory organic pollutants in coal chemical industry wastewater, poses a significant threat to human health and environmental quality. In this study, MnCexOy and MnFexOy catalysts were successfully synthesized by doping Ce3+ and Fe2+ into α-MnO2 at a molar ratio of 1∶10 and were applied to the process of catalytic ozonation for the degradation of quinoline. Additionally, a variety of characterization techniques were employed to elucidate the characteristics of the catalysts, including scanning electron microscopy, X-ray diffraction, Brunauer–Emmett–Teller (BET) analysis, X-ray photoelectron spectroscopy, H2-TPR, NH3-TPD. The results show that, in the catalytic ozonation system for quinoline removal, MnCexOy demonstrates excellent quinoline removal efficiency of 87.45%, which is higher than that of MnFexOy (78.83%) and unmodified α-MnO2 (62.67%). By introducing the surface hydroxyl masking agent HPO42−, the significant role of surface hydroxyl groups and oxygen vacancies in the catalytic degradation of quinoline by MnCexOy was further demonstrated. Exploring the surface characteristics of catalysts is beneficial for continued understanding of the active centers of catalysts. Research results will be helpful to the deep treatment and reuse of tailing water of coking wastewater.
研究领域:
环境科学
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催化材料科学
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DOI
高影响因子
International Journal of Environmental Research and Public Health
·
2019
·Vol. 16
·期 8
·1439
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IF 2.468
Yue Teng,Ke Yao,Wenbin Song,Yongjun Sun,Haoliang Liu,Zhiying Liu,Yanhua Xu
Cu-Mn-Ce@γ-Al2O3was prepared by incipient wetness impregnation and used to catalyze ozonation in a coal chemical wastewater-biotreated effluent. The preparation factors that considerably affected the catalytic performance of Cu-Mn-Ce@γ-Al2O3, specifically metal oxide loading percentage, calcination temperature, and calcination time, were examined. The catalyst was characterized by scanning electron microscopy, energy dispersive spectrometry, X-ray diffraction, and Brunauer-Emmett-Teller analysis. The optimal catalytic ozonation operating parameters, such as ozone dosage, catalyst dosage, pH, and reaction time, were also investigated. Results showed that an optimized catalyst consisted of 17.0% CuO, 3.0% MnO2, and 2.0% CeO2(wt.%). The optimal calcination temperature and calcination time were 600 °C and 5 h. The optimal catalytic ozonation operating parameters, including ozone dosage, catalyst dosage, pH, and reaction time, were 7, 80.0 mg/L, 20.0 mg/L, 7 and 50 min, respectively. The COD removal of biotreated effluent increased to 61% under these optimal operating conditions. Meanwhile, ozonation alone resulted in only 20% removal. This work proposes the use of easily available Cu-Mn-Ce@γ-Al2O3catalyst and might drive the advancement of catalytic ozonation for chemical wastewater purification.Keywords:catalyst;catalytic ozonation;coal chemical wastewater;advanced treatment
研究领域:
环境科学
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化学工程
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DOI
PubMed
高影响因子
ENVIRONMENTAL SCIENCE AND POLLUTION RESEARCH
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2022
·Vol. 29
·期 53
·80399-80410
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IF 5.19
Shu Xinpeng,Bi Huaqi,Wang Jun,Yang Jiaxin,Wang Jue,Liu Guangqing,Su Bensheng
Catalytic ozonation with supported metal oxides is a promising strategy for addressing refractory pollutants in wastewater. In this study, γ-Al 2 O 3 supported MnO x -CeO x catalysts (MC 1 , MC 2 , and MC 3 ) obtained at different calcination temperatures (400 °C, 550 °C, and 700 °C) were applied as effective catalysts for ozonation and explored the feasibility of the treatment of oxytetracycline (OTC) wastewater. Comparatively, the MC 2 possessed the highest molar ratios of Mn 3+ /Mn 4+ (1.60) and Ce 3+ /Ce 4+ (0.96), the largest surface area (273.8 m 2 g −1 ) with a petal-shaped structure, and most abundant surface hydroxyls (3.78 mmol g −1 ). These physicochemical characteristics benefited the surface reaction and resulted in the acceleration of ozone decomposition, electron transfer, and •OH generation, thereby improving the catalyst’s adsorption ability and catalytic activity. The combination with MC 2 increased the OTC and COD removal of the ozonation process from 59.1% and 29.0% to 94.7% and 83.3% in 25 min, respectively. By employing electron paramagnetic resonance (EPR) and radical quenching experiments, it was verified that •OH species generation promoted the mineralization of OTC. The possible degradation pathways of OTC were investigated through mass spectrometry, and the route consisted of dehydration, deamination, and demethylation. Moreover, during a 12-day continuous experiment, MC 2 catalyst exhibited excellent reusability and catalytic stability, with COD removal efficiencies above 80%.
研究领域:
环境科学
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化学工程
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PubMed
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2019
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IF 14.229
Yuxian Wang,Lulu Chen,Hongbin Cao,Zhaoxu Chi,Chunmao Chen,Xiaoguang Duan,Yongbing Xie,Fei Qi,Weiyu Song,Jian Liu,Shaobin Wang
La-based perovskites are catalytically active owing to the oxygen vacancies, redox metal centers of B sites and surface hydroxyl groups. Nevertheless, the insights into these active centers on environmental catalysis are still insufficient. In this study, hierarchical mixed oxides perovskite microspheres were synthesized for catalytic ozonation over oxalic acid and benzotriazole. LaMn 4 O x , with LaMnO 3-δ as the dominant crystal phase, demonstrated superior catalytic activity to Mn 2 O 3 and LaMnO 3 synthesized from citric acid sol-gel method. Temperature-programmed desorption of NH 3 (NH 3 -TPD) and pyridine-Fourier transform infrared spectroscopy (pyridine-FTIR) tests proved Lewis acid as the main acid type. Temperature-programmed reduction of H 2 (H 2 -TPR), O 2 -TPD and X-ray photoelectron spectroscopy (XPS) analysis indicated the presence of oxygen vacancies and mixed valences of Mn in the crystal structure facilitated the catalytic process. Moreover, the content of oxygen vacancy was calculated by iodometric titration method. With the aid of theoretical calculations, oxygen vacancies were found to exhibit a strong affinity toward ozone adsorption, where ozone molecules spontaneously dissociated into reactive oxygen species (ROS) such as O 2 − and 1 O 2 . The B site of Mn facilitated ozone decomposition by extending the O O bond of ozone due to the electron transfer from Mn 3+ /Mn 4+ redox cycle. In-situ EPR and quenching tests confirmed the contribution of O 2 − and 1 O 2 in benzotriazole degradation along with OH. This study stepped further to unveil the ozone adsorption/decomposition and ROS generation on nanoscale perovskite-based composites.
研究领域:
环境科学
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材料科学
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DOI
高影响因子
Small
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2025
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IF 12.1
Su Tang,Tao Zhong,Zhangnan Yao,Wei Qu,Ting Li,Huinan Zhao,Shuanghong Tian,Chun He
Frustrated Lewis pairs (FLPs) present new opportunities for the development of highly active spinel materials for the activation of stable molecules. Herein, a Ni and Co-based spinel with abundant FLPs sites (NiCo 2 O 4 -F) is synthesized through morphologic defect engineering and used for efficient catalytic ozonation CH 3 SH elimination. Characterization results reveal that the NiCo 2 O 4 -F with nanoflower structure exposes more surface oxygen vacancies (Ov), inducing local charge redistribution and forming active regions. Ov acts as Lewis basic sites, while the unsaturated coordinated Ni atoms (Ni uc ) act as Lewis acidic sites, and spatially ≈4.08 Å. The Ov···Ni uc FLPs function as “electron shuttles” in the reaction, facilitating specific adsorption of reactants via the dual acidic–basic reaction sites, thereby activating O 3 to generate ·O 2 − and 1 O 2 species to achieve deep oxidation of CH 3 SH. The resulting NiCo 2 O 4 -F catalyst exhibits an outstanding CH 3 SH removal efficiency of 94.4%, achieving a high mass activity (5.6 ppm mg −1 ), which is 70 times greater than that of commercial MnO 2 (0.08 ppm mg −1 ). This work presents a promising approach to developing sophisticated ozone catalysts by controllable construction of acid–base sites on spinel surface, enhancing the understanding of the role of FLPs structure in molecular activation.
研究领域:
材料科学
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环境科学
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催化化学
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DOI
PubMed
高影响因子
WATER SCIENCE AND TECHNOLOGY
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2024
·Vol. 89
·期 3
·823-837
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IF 2.5
Zhang Jie,Wu Zhaochang,Dong Ben,Ge Sijie,He Shilong
View large Download slide View large Download slide Close modal Quinoline inevitably remains in the effluent of coking wastewater treatment plants due to its bio-refractory nature, which might cause unfavorable effects on human and ecological environments. In this study, MnCe x O y was consciously synthesized by α -MnO 2 doped with Ce 3+ (Ce:Mn = 1:10) and employed as the ozonation catalyst for quinoline degradation. After that, the removal efficiency and mechanism of quinoline were systematically analyzed by characterizing the physicochemical properties of MnCe x O y , investigating free radicals and monitoring the solution pH. Results indicated that the removal rate of quinoline was greatly improved by the prepared MnCe x O y catalyst. Specifically, the removal efficiencies of quinoline could be 93.73, 62.57 and 43.76%, corresponding to MnCe x O y , α -MnO 2 and single ozonation systems, respectively. The radical scavenging tests demonstrated that • OH and • O 2 - were the dominant reactive oxygen species in the MnCe x O y ozonation system. Meanwhile, the contribution levels of • OH and • O 2 - to quinoline degradation were about 42 and 35%, respectively. The abundant surface hydroxyl groups and oxygen vacancies of the MnCe x O y catalyst were two important factors for decomposing molecular O 3 into more • OH and • O 2 - . This study could provide scientific support for the application of the MnCe x O y /O 3 system in degrading quinoline in bio-treated coking wastewater. MnCe x O y Ce 3+ , MnCe x O y • OH and • O 2 - MnCe x O y were successfully synthesized by α-MnO 2 doped with Ce 3+ . The by abundant oxygen vacancies and surface hydroxyl groups of the MnCe x O y catalyst enhanced its catalytic activity. • OH and • O 2 - formation contributed to quinoline degradation in the MnCe x O y ozonation system.
研究领域:
环境科学
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化学工程
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PubMed
高影响因子
Journal of Environmental Chemical Engineering
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2024
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IF 7.4
Zhaochang Wu,Sijie Ge,Ying Han,Mengchen Zong,Shilong He,Jie Zhang
Heterogeneous catalytic ozonation is widely used in advanced treatment for the removal of refractory organics from bio-treated coking wastewater. However, the effect of inorganic anions on quinoline removal by catalytic ozonation remains unclear. In this study, the effect of three inorganic anions including Cl - , Br - , SO 4 2- on performance and mechanism for quinoline removal by TiO 2 catalyst was investigated. Results indicated that all three anions have inhibitory effects on quinoline removal; meanwhile Br - exhibited the strongest inhibition. Furthermore, the effect of factors including initial solution pH, ozone concentration, catalyst dosage and coexistence of anions on Br - inhibition was explored. The Br - inhibition mechanism was further systematically analyzed by characterizing the physicochemical properties of catalysts and investigating free radicals and quinoline degradation pathways. The inhibition caused by Br - became stronger with the coexistence of SO 4 2- . The presence of Br - reduced the amount of oxygen vacancies and active sites on catalysts. Also, the activity and stability of catalysts decreased because of the Ti ions leaching, which was obviously exacerbated as the coexistence of SO 4 2- . Moreover, the Br - and SO 4 2- both could react with •OH to form abundant RHS (BrOH •- , Br• and Br 2 •- ) with low oxidative activity to further inhibit quinoline removal. The radical scavenging tests demonstrated that the main reactive oxygen species (ROS) was changed from •OH to O 2 •- and 1 O 2 in the catalytic ozonation system by the introduction of Br - and SO 4 2- . Meanwhile, brominated byproducts were found to be generated during the degradation of quinoline by GC-MS analysis.
研究领域:
环境科学
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化学工程
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DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
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2024
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IF 8.1
Jing Liu,Huiyu Dong,Carmen Sans,Xiangjuan Yuan
In this study, a series of boron (B) and oxygen (O) dual doped g-C 3 N 4 (BOCNx) composites with different boric acid dopant dosages were successfully synthesized through one-step thermal condensation method. Amongst, BOCN50 exhibited the best catalytic ozonation activity, achieving 97 % of iopamidol (IPM) degradation within 15 min and the highest k value (0.3166 min −1 ), which was 8 times higher than that of ozonation alone. Multiple characteristic techniques were used to explore the surface properties of BOCNx catalysts and it was found that B and O primarily coordinated in g-C 3 N 4 as the forms of C-O, C = O and B-N bonds. Further investigation in the structure–activity relationship of BOCNx catalyst indicated that the increasing contents of oxygen-containing functional groups and B-N bonds were linearly correlated with the IPM degradation rate. The results of scavenger experiments and ESR analysis demonstrated that the main reactive oxygen species involved were hydroxyl radicals, superoxide radicals, and singlet oxygen ( • OH, • O 2 − and 1 O 2 ). Additionally, up to 12 intermediate products of IPM during the reaction were detected, and the corresponding degradation pathways were elucidated. Finally, the structure of BOCN and the active sites for O 3 adsorption were determined by density functional theory (DFT) calculation, thus providing theoretical support for studying the mechanism of catalytic ozonation degradation.
研究领域:
环境科学
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材料科学
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化学工程
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高影响因子
APPLIED CATALYSIS A-GENERAL
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2015
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IF 3.942
Jun Chen,Shuanghong Tian,Jiang Lu,Ya Xiong
This study aims to provide a direction to tailor catalytic activity of catalyst by selectively exposing a crystal facet. Herein three sheet-like MgO materials with the primarily exposed crystal facet of (1 1 1), (1 1 0), (2 0 0) were prepared, respectively. Results show that the catalytic ozonation on each MgO substantially enhanced the removal of 4-chlorophenol and total organic carbon when compared with ozonation alone or that on traditional MgO. The pseudo first-order reaction constant of 4-chlorophenol removal in ozonation catalyzed by MgO(1 1 1), MgO(1 1 0), MgO(2 0 0) is 4.8, 2.5, 3.1 times higher than that in the single ozonation, respectively. When different dosage but the same surface area of MgO was applied, their catalytic activities changed as MgO(1 1 1) > MgO(1 1 0) > MgO(2 0 0). It indicates that the catalytic activity significantly depends on the crystal facet besides the surface area. That is because the drawbacks, such as edges, steps, and kinks, on each facet decreased in the order of (1 1 1) > (1 1 0) > (2 0 0). CO 2 -TPD and zeta potential measurement show that the drawbacks caused more and stronger surface basic groups in the form of hydroxyl and isolated oxygen due to the availability of more unsaturated coordination sites. These active basic centers make the easy formation of basic microenvironment near MgO particles and thus favor the ozonation. Finally, the catalytic mechanism was explored and compared by evaluating the ozone decomposition, qualitatively and quantitatively identifying hydroxyl radicals, and determining the ozone utilization efficiency. It reveals that MgO with more surface basic groups can enhance the transformation rate of ozone to hydroxyl radicals more efficiently. All these results show that MgO is a very potential ozonation catalyst and the catalytic activity can be tailored by exposing crystal facet with more drawbacks.
研究领域:
环境科学
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材料科学
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DOI
高影响因子
CHEMOSPHERE
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2021
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IF 7.086
Jiaxin Mu,Shangyi Li,Jing Wang,Xukai Li,Weirui Chen,Xinyuan Tong,Yiming Tang,Laisheng Li
Herein, we demonstrated the construction of three-dimensional (3D) cerium oxide (CeO x )/SBA-16 nanocomposites for efficient removal of bisphenol A (BPA) via a catalytic ozonation , with a high BPA mineralization up to 60.9% in 90 min. On one hand, the CeO x /SBA-16 mesoporous structured materials presented large surface area and uniform pore distribution, which was conducive to the adsorption of transformation by-products (TBPs) and then, the mass transfer. On the other hand, CeO x /SBA-16 could enhance the ozone utilization efficiency and meanwhile facilitate the formation of OH, the main reactive oxygen species . Through the exploration of dissoluble organic matters and the identification of the reaction intermediates, two BPA degradation pathways were proposed. This approach reported here will benefit the design and construction of mesoporous structured materials for catalytic elimination of hazards to remediate the environment.
研究领域:
环境科学
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材料科学
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DOI
PubMed
高影响因子
Journal of Cleaner Production
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2020
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IF 7.246
Zhengchu Yan,Jianxin Zhu,Xiuyi Hua,Dapeng Liang,Deming Dong,Zhiyong Guo,Na Zheng,Liwen Zhang
Polyvinyl alcohol (PVA) is widely used in industries and exists in corresponding effluents. As a refractory water-soluble polymer, PVA is hard to be biologically degraded and may cause membrane blockage problem in reclaiming the wastewater. Therefore, it is necessary for PVA-containing wastewater to be pretreated. In this study, the heterogeneous catalytic ozonation to degrade PVA was investigated. The composition of catalysts was screened, the catalyst preparation and the reaction conditions were optimized, and the degradation mechanism was discussed. According to the results, γ-alumina was selected as support, copper and manganese were selected as active components, and subsequently the complex catalyst, copper-oxygen-manganese/γ-alumina (CMA), was formed. The optimal preparation conditions of CMA were as follows: molar ratio of copper to manganese was 1:2 while loading rate was 4 wt%; copper and manganese loaded on γ-alumina successively by ultrasonic impregnation at 25 °C for 2.5 h, then dried at 100 °C for 4 h, and calcined at 500 °C for 4 h. When the initial concentration of PVA solution was 20 mg/L, the optimal dosage of the catalyst for catalytic ozonation was 100 mg/L. The removal rate of PVA reached 97.8% in 15 min at pH = 7, and 99.3% in 10 min at pH = 10. The leaching of the metals in CMA could be neglected, and the catalyst still had a satisfactory result after five cycles of reuse. The catalytic ozonation followed the mechanism of hydroxyl radical reaction. Although only a small fraction of PVA was mineralized after reaction, the long chains of PVA molecules were broken into smaller pieces. Therefore, it is an effective pretreatment method for reclaiming PVA-containing wastewater.
研究领域:
环境科学
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化学工程
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产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）