Among the numerous transition metal catalysts,manganese-based compounds are considered as promising peroxymonosulfate(PMS)catalysts due to their low cost and environmental friendliness,such as cryptomelane manganese o...Among the numerous transition metal catalysts,manganese-based compounds are considered as promising peroxymonosulfate(PMS)catalysts due to their low cost and environmental friendliness,such as cryptomelane manganese oxide(K_(2-x)Mn_(8)O_(16):abbreviation KMnO).However,the limited catalytic performance of KMnO limits its practical application.In this work,iron-doped KMnO(Fe-KMnO)was prepared by one-step hydrothermal method to optimize its catalytic performance.Compared with KMnO/PMS system,Fe-KMnO/PMS system possessed more excellent removal efficiency of tetracycline(TC).Meanwhile,the Fe-KMnO/PMS system also exhibited good practical application potential and excellent stability.The mechanism of Fe-KMnO activation of PMS was further analyzed in detail.It was found that Fe participated in the redox of high-valent Mn,which promoted the activation of PMS.Moreover,The Fe site as an adsorption site enhanced the TC enrichment ability of the catalyst,reducing the mass transfer resistance and further enhancing the TC removal ability of Fe-KMnO/PMS system.This work not only provides an excellent PMS catalyst,but also offers new insights into the mechanism of PMS activation by bimetallic manganese-based catalysts.展开更多
As persulfate(S_(2)O_(8)^(2-))is being increasingly used as an alternative oxidizing agent,developing lowcost and eco-friendly catalysts for efficient S_(2)O_(8)^(2-)activation is potentially useful for the treatment ...As persulfate(S_(2)O_(8)^(2-))is being increasingly used as an alternative oxidizing agent,developing lowcost and eco-friendly catalysts for efficient S_(2)O_(8)^(2-)activation is potentially useful for the treatment of wastewater containing refractory organic pollutant.In this study,the degradative features and mechanisms of carbamazepine(CBZ)were systematically investigated in a novel FeS-S_(2)O_(8)^(2-)process under near-neutral conditions.The results exhibited that CBZ can be effectively eliminated by the FeS-S_(2)O_(8)^(2-)process and the optimal conditions were:250 mg/L FeS,0.5 mmol/L S_(2)O_(8)^(2-),and pH=6.0.The existence of Cl^(−)(1 and 50 mmol/L)has little influence on the CBZ elimination,while both HCO_(3)^(−) and HPO_(4)^(2−)(1 and 50 mmol/L)significantly suppressed the CBZ removal in the FeS-S_(2)O_(8)^(2-)process.CBZ could be degraded via a radical mechanism in the FeS-S_(2)O_(8)^(2-)process,the working radical species(i.e.,SO_(4)•−and•OH)were efficiently formed via the promoted decomposition of S_(2)O_(8)^(2-)by the surface Fe2+on the FeS and the dissolved ferrous ions in solution.Based on the identified oxidized products and Fukui index calculations,a possible degradation pathway of CBZ was speculated.More importantly,a two-stage oxidation mechanism of CBZ elimination was speculated in the FeS-S_(2)O_(8)^(2-)process,the activation of S_(2)O_(8)^(2-)by the surface-active Fe(II)of FeS dominated in the initial 5 min,while homogeneous oxidation reactions played more essential parts than others in the following reaction stage(5–60 min).Overall,this study demonstrated that the FeS-S_(2)O_(8)^(2-)process is capable of removing CBZ from water efficiently.展开更多
Rational structure design and regulation are of paramount importance for obtaining electrode materials with desirable electrochemical performance.Here,a novel binder-free electrode with the hollow Co_(9)S_(8) core@mul...Rational structure design and regulation are of paramount importance for obtaining electrode materials with desirable electrochemical performance.Here,a novel binder-free electrode with the hollow Co_(9)S_(8) core@multi-shell structure(CS-x@MXene@Bi_(2)O_(3))derived from metal-organic frameworks(MOFs)precursor is well designed by the electrospinning,sulfuration,carbonization,and hydrothermal processes.In this architecture,the concentration of Co_(9)S_(8)(CS-x)is optimized for an ideal flexible substrate,which alleviates the dimensional variation for long cycle life.The unique cores and the MXene flakes engineered by Bi_(2)O_(3) multiple shells can be responsible for the superior characteristics,including a fast electronic pathway,large specific surface area,enhanced electrical conductivity,and improved electrochemical performance.As expected,the obtained CS-2@MXene@Bi_(2)O_(3) binder-free electrode exhibits a high discharge capacitance of 646.1 F g^(–1)(1 A g^(–1)).Two binder-free electrodes can be assembled into a solid-state supercapacitor with desirable energy and power density,and long-term cyclic stability is demonstrated through 5000 cycles.Given these advantages,the CS-2@MXene@Bi_(2)O_(3) is selected as the electrode in a foldable supercapacitor.More importantly,the specific capacitance is reserved after various deformations.Therefore,it is expected that binder-free electrode materials with the unique core@shell structure design could be applied in wearable and portable energy conversion devices.展开更多
Nanosized solid superacids SO_(4)^(2−)/TiO_(2)and S_(2)O_(8)^(2)−/TiO_(2),as well as MCM-41-supported SO_(4)^(2−)/ZrO_(2),were prepared.Their structures,acidities,and catalytic activities were investigated and compare...Nanosized solid superacids SO_(4)^(2−)/TiO_(2)and S_(2)O_(8)^(2)−/TiO_(2),as well as MCM-41-supported SO_(4)^(2−)/ZrO_(2),were prepared.Their structures,acidities,and catalytic activities were investigated and compared using XRD,N2 adsorption-desorption,and in situ FTIR-pyridine adsorption,as well as an evaluation reaction with pseudoionone cyclization.The results showed that SO_(4)^(2−)/TiO_(2)and S_(2)O_(8)^(2)−/TiO_(2)possess not only nanosized particles with diameters<7.0 nm,a BET sur-face greater than 140 cm2/g and relatively regular mesostruc-tures with pores around 4.0 nm,but also a pure anatase phase and strong acidity.Different from the Lewis acid nature of SO_(4)^(2−)/ZrO_(2)/MCM-41,SO_(4)^(2−)/TiO_(2)and S_(2)O_(8)^(2)−/TiO_(2)exhibit mainly Brønsted acidities.The strongest Brønsted acid sites were produced on SO_(4)^(2−)/TiO_(2)promoted with H2SO4,while Lewis acid sites on S_(2)O_(8)^(2)−/TiO_(2)even stronger than those on SO_(4)^(2−)/ZrO_(2)/MCM-41 were generated when persulfate solu-tion was used as sulfating agent.Because of their distinct acid natures,SO_(4)^(2−)/TiO_(2)and S_(2)O_(8)^(2)−/TiO_(2)exhibited catalytic activities for the cyclization of pseudoionone that were much higher than that of SO_(4)^(2−)/ZrO_(2)/MCM-41.It can be concluded that the existence of more Brønsted acid sites was favorable for proton participation in the cyclization reaction.展开更多
基金supported by the National Natural Science Foundation of China (21806115)Sichuan Science and Technology Program (2020YJ0149)+1 种基金the Power Construction of China (P42819,DJ-ZDXM-2019-42)the Supported by Sichuan Science and Technology Program (2021ZDZX0012)。
文摘Among the numerous transition metal catalysts,manganese-based compounds are considered as promising peroxymonosulfate(PMS)catalysts due to their low cost and environmental friendliness,such as cryptomelane manganese oxide(K_(2-x)Mn_(8)O_(16):abbreviation KMnO).However,the limited catalytic performance of KMnO limits its practical application.In this work,iron-doped KMnO(Fe-KMnO)was prepared by one-step hydrothermal method to optimize its catalytic performance.Compared with KMnO/PMS system,Fe-KMnO/PMS system possessed more excellent removal efficiency of tetracycline(TC).Meanwhile,the Fe-KMnO/PMS system also exhibited good practical application potential and excellent stability.The mechanism of Fe-KMnO activation of PMS was further analyzed in detail.It was found that Fe participated in the redox of high-valent Mn,which promoted the activation of PMS.Moreover,The Fe site as an adsorption site enhanced the TC enrichment ability of the catalyst,reducing the mass transfer resistance and further enhancing the TC removal ability of Fe-KMnO/PMS system.This work not only provides an excellent PMS catalyst,but also offers new insights into the mechanism of PMS activation by bimetallic manganese-based catalysts.
基金the National Natural Science Foundation of China(No.52100060)the Natural Science Foundation of Hubei Province,China(No.2020CFB383)for the financial support。
文摘As persulfate(S_(2)O_(8)^(2-))is being increasingly used as an alternative oxidizing agent,developing lowcost and eco-friendly catalysts for efficient S_(2)O_(8)^(2-)activation is potentially useful for the treatment of wastewater containing refractory organic pollutant.In this study,the degradative features and mechanisms of carbamazepine(CBZ)were systematically investigated in a novel FeS-S_(2)O_(8)^(2-)process under near-neutral conditions.The results exhibited that CBZ can be effectively eliminated by the FeS-S_(2)O_(8)^(2-)process and the optimal conditions were:250 mg/L FeS,0.5 mmol/L S_(2)O_(8)^(2-),and pH=6.0.The existence of Cl^(−)(1 and 50 mmol/L)has little influence on the CBZ elimination,while both HCO_(3)^(−) and HPO_(4)^(2−)(1 and 50 mmol/L)significantly suppressed the CBZ removal in the FeS-S_(2)O_(8)^(2-)process.CBZ could be degraded via a radical mechanism in the FeS-S_(2)O_(8)^(2-)process,the working radical species(i.e.,SO_(4)•−and•OH)were efficiently formed via the promoted decomposition of S_(2)O_(8)^(2-)by the surface Fe2+on the FeS and the dissolved ferrous ions in solution.Based on the identified oxidized products and Fukui index calculations,a possible degradation pathway of CBZ was speculated.More importantly,a two-stage oxidation mechanism of CBZ elimination was speculated in the FeS-S_(2)O_(8)^(2-)process,the activation of S_(2)O_(8)^(2-)by the surface-active Fe(II)of FeS dominated in the initial 5 min,while homogeneous oxidation reactions played more essential parts than others in the following reaction stage(5–60 min).Overall,this study demonstrated that the FeS-S_(2)O_(8)^(2-)process is capable of removing CBZ from water efficiently.
基金support from the National Natural Science Foundation of China(no.52072307)。
文摘Rational structure design and regulation are of paramount importance for obtaining electrode materials with desirable electrochemical performance.Here,a novel binder-free electrode with the hollow Co_(9)S_(8) core@multi-shell structure(CS-x@MXene@Bi_(2)O_(3))derived from metal-organic frameworks(MOFs)precursor is well designed by the electrospinning,sulfuration,carbonization,and hydrothermal processes.In this architecture,the concentration of Co_(9)S_(8)(CS-x)is optimized for an ideal flexible substrate,which alleviates the dimensional variation for long cycle life.The unique cores and the MXene flakes engineered by Bi_(2)O_(3) multiple shells can be responsible for the superior characteristics,including a fast electronic pathway,large specific surface area,enhanced electrical conductivity,and improved electrochemical performance.As expected,the obtained CS-2@MXene@Bi_(2)O_(3) binder-free electrode exhibits a high discharge capacitance of 646.1 F g^(–1)(1 A g^(–1)).Two binder-free electrodes can be assembled into a solid-state supercapacitor with desirable energy and power density,and long-term cyclic stability is demonstrated through 5000 cycles.Given these advantages,the CS-2@MXene@Bi_(2)O_(3) is selected as the electrode in a foldable supercapacitor.More importantly,the specific capacitance is reserved after various deformations.Therefore,it is expected that binder-free electrode materials with the unique core@shell structure design could be applied in wearable and portable energy conversion devices.
文摘Nanosized solid superacids SO_(4)^(2−)/TiO_(2)and S_(2)O_(8)^(2)−/TiO_(2),as well as MCM-41-supported SO_(4)^(2−)/ZrO_(2),were prepared.Their structures,acidities,and catalytic activities were investigated and compared using XRD,N2 adsorption-desorption,and in situ FTIR-pyridine adsorption,as well as an evaluation reaction with pseudoionone cyclization.The results showed that SO_(4)^(2−)/TiO_(2)and S_(2)O_(8)^(2)−/TiO_(2)possess not only nanosized particles with diameters<7.0 nm,a BET sur-face greater than 140 cm2/g and relatively regular mesostruc-tures with pores around 4.0 nm,but also a pure anatase phase and strong acidity.Different from the Lewis acid nature of SO_(4)^(2−)/ZrO_(2)/MCM-41,SO_(4)^(2−)/TiO_(2)and S_(2)O_(8)^(2)−/TiO_(2)exhibit mainly Brønsted acidities.The strongest Brønsted acid sites were produced on SO_(4)^(2−)/TiO_(2)promoted with H2SO4,while Lewis acid sites on S_(2)O_(8)^(2)−/TiO_(2)even stronger than those on SO_(4)^(2−)/ZrO_(2)/MCM-41 were generated when persulfate solu-tion was used as sulfating agent.Because of their distinct acid natures,SO_(4)^(2−)/TiO_(2)and S_(2)O_(8)^(2)−/TiO_(2)exhibited catalytic activities for the cyclization of pseudoionone that were much higher than that of SO_(4)^(2−)/ZrO_(2)/MCM-41.It can be concluded that the existence of more Brønsted acid sites was favorable for proton participation in the cyclization reaction.
